PAPERMAKING RAW MATERIALS AND THEIR CHARACTERISTICS

By Dr. Chhaya Sharma

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

CONFORMABLE

DEVELOP STRONG BONDS

Paper is a felted sheet of Fiber. The basic requirement of fibers to be useful for papermaking, Conformable & develop strong bonds The degree of fiber conformability can be measured as sheet formation, while the degree of bonding is measured by the burst or tensile strength of the sheet. Some pulps are useless for papermaking in their raw state because the fibers are relatively non-conformable and non-bonding. For example, cotton and linen rags (which are still used to produce high quality, durable papers) must be mechanically treated to develop the desired properties.

Table. Properties of Cellulosic Fibers high tensile strength flexibility, conformability resistance to plastic deformation water insoluble hydrophilic wide range of dimensions inherent bonding ability ability to absorb modifying additives chemically stable relatively colorless (white)

The hydrophilic nature of cellulosic fibers plays an important role, since the papermaking process occurs in an aqueous medium. The fibers readily absorb water and are easily dispersed in a water suspension. When wet fibers are brought together during the sheet-forming operation, bonding is promoted by the polar attraction of the water molecules for each other and for the hydroxyl groups covering the cellulose surface. As the water is evaporated the hydroxyl groups of cellulose surfaces ultimately link together by means of hydrogen bonds.

Illustrating different levels of hydrogen bonding (A) Loosely through water molecules (B) More tightly through monolayer of water molecules (C) Directly

While individual cellulosic fibers generally have high tensile strength, the strength parameters of paper are also dependent on the bonds between fibers.
Beating or refining tends to optimize bonding at the expense of individual fibers strength.

Of course, the original fiber strength depends on the raw material and the method of pulping.
Since most paper products utilize non-fibrous additives in their manufacture, the ability of the pulp fibers to absorb or retain a wide variety of modifying materials is important.

FIBER MORPHOLOGY
INTRODUCTION
Fibers constitute the basic raw material for paper. This category of fiber includes nonplant fibers and plant fibers.

Non Plant Fibers

Non plant fibers can be of following type:

Animal Fibers (wood, hair, silk)

Mineral Fibers (asbestos, glass)

Synthetic (Rayon, Nylon etc.)
All these nonplant fibers are incorporated only in some speciality products.

Plant Fibers
Almost all growing plants have been tried for pulp & papermaking, and technically it has been possible to produce satisfactory products also. However economics plays an important role here and the consideration of collection, storage, and processing sometimes put limit to the use of some materials.

All these fibrous raw materials range from tiny grass plants to all trees. Since they all are the metabolic products of living organism, it is certain that they will have infinite variations due to genetic and environmental factors. There is a need to understand scientifically and technically these raw materials w.r.t its anatomical and morphological characteristics in order to obtain a correct and optimized utilization.

THE PLANT KINGDOM Plants kingdom can be divided into 4 main divisions:
Thallophytes Bryophytes Pteridophytes

Spermatophytes

These seed bearing plants are only of use to pulp and paper maker.

Spermatophytes (Seed bearing plants)

Gymnosperm (Naked seeds) Conifers, Evergreen, Softwood All woody

Angiosperms (Covered seeds)

Monocotyledonous Non woody

Dicotyledonous Woody or Non-woody

DEFINITION OF WOOD
Classifying a plant as woody means that the following criteria must be fulfilled. Plants living for many years. (Perennials) The stem must not die back every year. Even if the roots may survive and produce a stem next year, these plants are not classified as woody. Plants must possess a vascular system and have a specialized conducting system. (Xylem and phloem). A cambium between xylem and phloem producing secondary growth.

PRIMARY GROWTH The woody stem has an axial core of vascular tissues, protected by the bark on the outside.

When a tree grows it increases with age both in length and diameter.
The growth is due to the activity of specialized cells called MERISTEMS (greek means divisible). The meristems are situated at the tips of the shoots and the roots. These cells divide, grow, differentiate, and cause the extension of the plant.

SECONDARY GROWTH
XYLEM-PHLOEM

A tree grows in thickness by the activity of the CAMBIUM, a single layer of living meristematic cells. These cells produce sapwood or XYLEM on the inside and bark or PHLOEM on the outside. As the tree grows larger, the inner core of the SECONDARY WOOD (xylem) ceases to function actively. This part called the HEARTWOOD functions only as mechanical support. In many species of wood the heartwood is darker than the outside active part called the SAPWOOD. That part is a complex tissue both strengthening and conducting water and solutes. The main function of the phloem (the INNER BARK) is transport of photosynthetic products.

Outer bark Inner bark

Plant organization
Three major tissue system: - 1. Dermal 2. Vascular 3. Fundamental.

Dermal: In its early life plant is covered by one to several layers of cells called epidermis which function in photosynthesis, gives protection, regulate gas exchange. Epidermal cells are impregnated with hydrophobic wax like substance cut in.

Vascular System: It is the conducting or circulatory system of higher plants and is composed of two major complex system xylem and phloem. The xylem functions principally in movement of water, soil nutrients and stored food from root system upwards to developing leaves and buds. Hormones and photosynthates manufactured in trees crown are then transported downward direction by phloem to developing stem and roots. Another function of xylem in woody plants is to provide mechanical support. This role is fulfilled by Fiber cells which are dead and heavily lignified at maturity.

Fundamental System: These cells are relatively unspecialized and can have various physiological functions. These cells are commonly referred as ground tissue also often acts as a sort of filler tissue. These categories can be distinguished.

Parenchyma. Collenchyma. Sclerenchyma.

Parenchyma: In softwoods and hardwoods parenchyma are small, often living cells functioning for photosynthesis, storage, secretion and wound healing. They are commonly thin walled, but in central regions of stems and roots may be thick walled and heavily lignified. They may also accumulate crystals (e.g. cal. oxalates, Tannins (polyphenols) or food materials like starch fats, oil etc.

In monocots (non wood) parenchyma are much more varied in size, and can be as large as fibers in some plants.

Collehchyma: They have a large similarity to that of parenchyma, however, these cells are a bit longer and have special wall thickening. The cell walls are rich in pectin. These are often located near the surface of young stems and in leaf veins. They are not of any relevance to wood pulping but are present in some grasses in large volumes along with parenchyma and it is desirable to separate them from fiber cells e.g. bagasse.

Sclerenchyma: These are usually dead cells at maturity; they are thick walled and heavily lignified functioning primarily for mechanical support.
There are two types of cells which can be distinguished (a) fiber (b) sclereids. Fibers are similar to xylem, sclerenchyma fibers are extra xylary in location. Such as phloem of dicots or bast fibers (jute, help etc.) present in vicinity of vascular bundles. Sclereids are variably shaped cells often branched .

They give hardness and rigidity to tissues like phloem, leaves, seed coats, shells etc.
In wood pulping they may enter by way of bark, this may give rise to stone cell problem or dirt or speck in high quality papers.

Sl. No.

Pulp

FIBERS

Parenchyma

Vessels

Epidermal Cells

Length

Width

Special Features (5)

Flat, ribbonlike and twisted, occasionally with torn, base

(1)
i) Rag

(2)

(3)
2900 (780-8000) mostly incomplete

(4)
24 (10-34 )

(6)
-

(7) -

(8) -

STRUCTURE OF SOFTWOOD

STRUCTURE OF SOFTWOOD
More than 90% of the cells in softwood are tracheids. A TRACHEID is a hollow tubular cell with closed pointed ends with a major function as a liquid conducting element. The cavity inside the cell is called Lumen. The length of the tracheids ranges from 2.5 to 7 mm. (Average is 3.5 mm). The width is more constant and ranges from 30 to 45 um. This gives average length versus diameter 100:1 for softwood fibers. The tracheids in the summerwood develop thick walls and a narrow lumen and may be termed FIBER-TRACHEID. Softwood fibbers are highly appreciated because of their fiber length and conformability, and the source of so called long fibered wood pulps. Neighbouring tracheids are joined by so called Bordered pits for inter fiber conduction. Usually the bordered pits are present only on the radial walls of the tracheids.

STRUCTURE OF SOFTWOOD Major types of cell composing softwood are listed below. Orientation of Cells Major Axis in the Tree.

Vertical (Longitudinal)

Horizontal (Radial)

1. Trachied (Fiber)

1. Ray Trachied

2. Storage parenchyma

2. Storage parenchyma

3. Epithetial cells

3. Epithelial cells

Wall Anatomy

Softwood fiber wall are interrupted by pits which makes the major path-way for upward or interfiber condution of liquid sap. Which are called bordered pits. Some times they have another wall making called spiral thickening.

(A & . B) Softpine., (C) Hardpine, (D) Doughlasfire

Sl. No. Pulp FIBERS Parenchyma Vessels Epidermal Cells

Length

Width

Special Features

(1) viii)

(2) Spruce (mechanical)

(3) Incomplete

(4) 40 (30-60 )

(5) Tracheids with large uniseriate bordered pita and piceoid cross-field pitting

(6) Torn ray attached tracheids cells to

(7) -

(8) -

HARDWOODS (DICOTYLEDONS)

The botanical group of plants larger than that of softwoods. Hardwoods grow in almost all regions of the world, from temperated to tropical zones. They have to be adaptable to variable growing conditions and have therefore a more complicated anatomy than the softwoods. Hardwoods are rapidly growing trees and consequently they need an effective conducting system. The water conducting function is undertaken by so called vessel elements. Thus hardwood is called porous wood. In hardwoods the annual rings are visible mainly due to the regularity of the vessels. Large vessels are usually present in the springwood zone and later they are gradually decreasing. This pattern is very characteristics for each species

STRUCTURE OF HARDWOOD Major cell types comparing most hardwoods used for pulp and paper are listed below. Orientation of Cells Major Axis in the Tree. Vertical (Longitudinal) 1. Fiber Cells a) Libriform fibers b) Fiber Trachieds Horizontal (Radial) 1. Ray parenchyma a) Horizontal Parenchyma b) Vertical Orientation

2. Storage parenchyma 3. Vessel Elements

The vessels are non fibrous tube like elements running vertically in the tree. They have large diameter compared to the fibers. They are joined together end-to-end and appear as pores in the cross section.

Cross-sectional section of Betula (Birch) A. Vessels, B. Fibers, C. Medullary rays

Two-dimensional view of Betula (Birch)

The hardwood fibers are true fibers and are termed libriform fibers (liber means hard tissue)
Libriform fibers only have a reinforcing function, and are not water leading. Usually they have thick walls, a narrow lumen and reduced pitting. The average fiber length is 1 to 1.6 mm (in wood pulps ax. Only 1 mm). Hardwood fibers are referred to as short fibers. Many species (like oak and eucalyptus) also have socalled vasicentric tracheids, short irregular fibrous cells with small bordered pits. They are usually surrounding the large vessels.

(A,B & C - Fiber) (D Vessel) (E,F,G,&H Parenchyma)

Sl. No. Pulp Length FIBERS Width Special Features Parenchyma Vessels Epidermal Cells

(1) vi)

(2) Hard wood (chemical)

(3) 850 (3501300 )

(4) 25 (15-45 )

(5) Fibers markedly variable in width often with abruptly pointed ends. Septa sometimes present

(6) Comparatively few. Length 120(40-320 ). Width 35 (2070 )

(7) Present. Width 170 (70280 )

(8) -

STRUCTURE OF NONWOOD
The sugar cane stalk, as it enters the sugar mill after the leaves, dirt and extraneous matter are removed, contains 3 main parts pith, fiber bundles and epidermis. They behave differently during pulping processes because they each have different physical and to some extent chemical characteristics.

Pith or center portion

Approximately 50% of the oven dry weight of stalk consists of pith or parenchyma cells which do not have fibrous value and located throughout the cross section with individual fiber bundles embedded in this pith. Within the center portion of stalk, also there are scattered fiber bundles.

The fiber of the Ring

Approximately 50% of the oven dry weight of stalk consists of high quality fiber bundles concentrated in the hard, dense rind of stalk. The fiber bundles located in this rind layer are all oriented parallel to the axis of stalk except for these at the nodes, and they give rigidity to the stalk. The fiber in the rind layer are longer than the scattered fibrous elements in the interior of stalk and are more resistant to chemical action than either the pith or interior fiber or node fibers.

The Epidermis
Outside the rind layer of sugar cane stalk at the surfaces is found a thin, but very dense, epidermis. It contains waxes and other materials and is very resistant to pulping. The epidermis layer usually represents about 5% of dry weight of cane stalk and is perhaps the most undesirable element of stalk so far pulping is concerned. If it is not removed during depithing it leaves troublesome residue in the finished pulp, usually appearing as dark specks.

Morphological characteristics of Bagasse Pulp

Sl. No. Pulp FIBERS Parenchyma Vessels Epidermal Cells

Length

Width

Special Features

(1)
iii)

(2)
Bagasse

(3)
1750 (250-4 000)

(4)
23 (10-60 )

(5)
Compressed areas with transverse marking common. Fibre pits fairly numerous

(6)
Abundant Length 375 (100-900). Width 100 (30-180)

(7)
Present Width 1001 (30-220 )

(8)
Few with undulating margins

MAIN FUNCTION OF THE VARIOUS CELL TYPES IS WOOD.

Softwood
Mechanical function Trachieds

Hardwood
Libriform fibers Fiber trachied

Conductivity Function

Early wood Trachied Ray trachied

Vessel Vessel trachied

Storing function

Ray parenchyma Longitudinal Parenchyma

Ray parenchyma Longitudinal Parenchyma

Secretioning Function

Epithetial

Epithetial cells

Sl. No

Pulp

FIBERS

Parenchyma

Vessels

Epidermal Cells

Length

Width

Special Features

(1)

(2)

(3)

(4)

(5)

(6)

(7)

(8)

ii)

Bamboo

2100 (4005 000 )

15 (5-40)

Compres sed areas with transvers e markings common, Pitting extremely sparse

Abundant. Length 110 (30-500 ). Width 35.(10-60 )

Present.Wi dth 120 (40-250)

Rare with wavy margins

COMPARISON BETWEEN SOFTWOOD, HARDWOOD AND NON-WOOD

Soft wood Pine Cell dimensions Trachieds/Fiber Length mm Diameter m Vessels Length mm Diameter m Cell percentage Trachieds/Fibers% Vessel % Longitudinal parenchyma % Ray parenchyma % 3.1 30 Nonwood Bamboo Hardwood (Tropical zone) Tectona grandis

2.7-4.0 15

0.7-1.4 ---

-----

650 120

--50-370

93.1 --1.4-5.8 5.5

58 16 -----

66.3 11.6 11.6 15.5

PAPERMAKING FIBER
A plant fiber, to pulp and paper maker is an elongated or tubular, cylindrical very small cell obtained from certain plants or parts of plants. Its diameter is quite thin and considered to be microscopic, i. e. less than 0.1 mm (100 m).

However its length can be significant varying from about 0.5 mm to over 120 mm. for common paper making fibers, the length/diameter (L/D) ratio lies in the range of 50-200:1.
Fibers from different sources have different physical properties, length, width, wall thickness, cavity diameter in addition to their varying amounts of three main constituents i. e. Cellulose, Hemicellulose and Lignin.

ULTRA STRUCTURE AND CHEMISTRY

The fibers a built up of several different layers and has a cavity inside.

The internal organization of fiber wall, the percentage chemical present in it and its dimensions are very important feature in deciding the pulp and papermaking characteristics of fibers.
The internal organization of the fiber wall is referred to as its "ultra structure". The fiber wall is a composite of organic materials.

The organic materials are the polymers, which with special arrangement in producing a complex, highly ordered material with distinct structural and mechanical properties.

Framework Substance Cellulose

The skeletal or framework substance of all wood cell walls is "cellulose"-a straight - chain, unbranched, hydrophilic polysaccharide-composed of repeating sugar units or monomers. The latter are all the same - a six carbon ring sugar, "glucose"'. The number of these monomers in a single cellulose molecule or polymer (degree of polymerization or DP) averages about 10,000 in wood. Structurally, due to the particular linkage of these monomers, the smallest identically repeating segment of the chain is actually a pair of adjacent glucose units known as the cellobiose unit.

A measure of the order in cellulose is referred to as its "index of order" and is related to the amount of so-called "crystalline" cellulose. Highly ordered regions are thus referred to as "crystallites", and the zones where cellulose is not so ordered are termed "amorphous".
Amorphous Regions

Crystalline Regions
Schematic of Molecular organization within a Cellulose Microfibril

The order in wood cellulose is highly variable and depends on tree age, the particular wood tissue, and the tissue's overall chemical composition.
It is an important parameter, however, affecting the physical and chemical properties of both wood and pulp fibers. More specifically, higher degrees of order (crystallinity) normally imply higher (fiber) density and hardness, stiffness, and rigidity, tensile strength, and dimensional stability. At the same time, other factors are lower, namely, fiber flexibility, toughness, elongation, swelling on water absorption, and chemical reactivity. Paper properties will be affected by these fiber properties.

Fibers of higher stiffness and rigidity will produce bulkier papers.

Fibers with greater dimensional stability will produce papers of greater dimensional stability (lower curl potential). Cellulose molecules are aggregated laterally to form threadlike structures called microfibrils, which are visible only with an electron microscope. The length of microfibrils is not well defined, but their diameters are reported to measure about 10-20 nm.

Organization of Cell Wall Layers

Microfibril occurs macrofibril. in small bundles or

These, in turn, can be organized into thin sheets or lamellae which give the wall a layered architecture.
At the fiber surface, the microfibril forms a thin, net like covering surface, the primary wall. However, in the bulk of fiber wall or secondary wall, the microfibrils occur in parallel arrays, or sheets of preferred orientation which is spiral about the fiber, producing layered construction. The orientation of different wall lamellae from the fiber axis is termed as microfibril angle.

Primary Wall
In the thin primary wall, microfibrils form a more or less irregular, interwoven pattern. This arrangement facilitates the walls expansion activity, during fiber elongation. Microfibrils in the outer part of the primary wall (the first formed part) tend to be oriented somewhat along the fiber axis. In the innermost part, next to the outer part of the secondary wall, they are oriented more transversely, i.e., at a high microfibril angle. The cellulose content of the primary wall is difficult to determine.

However, it has been estimated to be about 10% in the living tree and is thought to be embedded in a matrix of pectic materials (largely carbohydrate derivatives of polygalacturonic acid), other hemicelluloses, and lignin.
The DP of cellulose here is thought to be about 5000.

Secondary Wall
In the inner most part of primary wall the cellulose microfibril begin to exhibit an ordered arrangement.

The layers have three different layers S1, S2 and S3.

In S1 (0.1 0.2 m thick) the microfibril have large angel to the fiber i.e. 55 75 oC, S2 makes a thick layer about 2 10 m thick and has microfibril orientation close to fiber axis. In S2 the fibrillar angel is typically 5o and 20 oC. S3 layer has similar construction to that of S1 it is thinner than S1 (0.07-0.08 m) and has microfibril angle between 60o 90o.

Matrix Material Hemicellulose The cellulose framework is penetrated and encased by, but not bonded to, carbohydrates known as "hemicelluloses". These materials differ substantially from cellulose in that they are composed of combinations of fivecarbon and six-carbon ring sugars, possess side groups on the chain molecule, and are amorphous in the fiber wall. Also, the DP of these sugars is in the range of only 50-300. Softwood hemicelluloses are largely galactoglucomannans while those in hardwoods are mostly xylan. In both cases, they serve as a supportive matrix for the cellulose microfibrils and appear to have a relatively uniform distribution across the fiber wall.

In high-purity pulps (dissolving grades or "high-alpha" pulps) it is common practice to remove most of the hemicelluloses as well as lignin. However, in paper-grade pulps, hemicelluloses are retained as much as possible to maintain pulp yield and to promote desirable fiber properties. More specifically, hemicelluloses are very hydrophilic (waterloving) and play a major role in the fiber's ability to adsorb water during beating and refining. Consequently, they promote internal lubrication of the fiber, leading to improved flexibility, ease of mechanical refining, and increase sheet density. Hemicelluloses also act as an interfiber bonding agent or adhesive to strengthen paper. However, during pulp drying them also tend to help harden or stiffen the fibers (hornification) which can impede-subsequent pulp rehydration.

The types and simplified structures of the major hemicelluloses in wood

EXTRANEOUS SUBSTANCES
In addition to the major chemical components of the wood fiber, the wall complex usually contains small amounts of various extraneous, largely organic materials which are known simply as 'extractives". As this name implies, these substances can be extracted from the wood tissue or fiber wall with either water or with various organic solvents, the choice of solvents varying with the nature of the extractive. Typical solvents include alcohols, ethers, acetone, and others.

. Major Classes of Wood Extractives CLASSES 1. ALIPHATIC Fats PRIMARY LOCATION RESIN CANAL COMPLEX PARENCHYMA Softwood Hardwood RESIN CANAL COMPLEX PARENCHYMA Hardwood

Waxes
Sterols 2. TERPENES/TERPENOIDS Volatile monoterpenes Terpenoid Resin acids Other (high melting point) PHENOLIC COMPOUNDS Simple phenols Lignans Stilbenes Tropolones Polyphenols Hydrolyzable tannins Flavonoids Condensed tannins

-Mostly fatty acid esters (mainly triglycerides) -Esters of long-chain aliphatic alcohols or terpenoid alcohols -Esters of steroid compounds

3.

HEARTWOOD Substituted C6 or C3C6 units Two C.3C6 units (e.g., conidendrin spruce, hemlock) Extremely reactive (e.g., pinosylvins - pines) Fungicidal properties (e.g., thujaplicin - w. redcedar) Restricted essentially to hardwoods e.g., taxifolin - Douglas-fir, larch Flavonoid polymers; essentially in softwoods

Softwoods Hardwoods

"Compose "nonsaponitiables", which contribute to pitch problems in pulping.

Of concern to the wood technologist, extractives are largely the source of wood color and odor and can have a strong influence on its liquid/gas permeability, dimensional stability natural durability, density, and strength properties. The pulp maker is not generally concerned so directly with extractives as they are found in the wood.
However, the variable effects that extractives can have on wood chipping refining, penetrability and diffusion of pulping liquors, by-product yield type from pulping, cost/difficulty of extractives control in pulping/bleaching/washing, and the effects of residual extractives or pitch in the final pulp are direct concerns of the pulp mill and ultimately of the pulp converter. The relative importance of wood species and extractives type will vary with the particular pulping process (e.g., mechanical or chemical, kraft or sulfite).

Incrustant - Lignin
The major constituent of the fiber wall is "lignin", an amorphous, highly branched, and three dimensional, phenolic polymers. Lignin is manufactured by maturing fibers (or other wood cells) and permeates the fiber walls and intercellular regions (middle lamellae). In mature xylem, lignin lends rigidity and cohesiveness to wood tissue as a whole. On a weight basis lignin comprises about 25-35% of normal softwood xylem, and about 15-25% of hardwood xylem.

 Lignin constitutes 80% or more by weight of the middle lamella in mature xylem. However, most of the wood lignin (two thirds or more) is located in the wood cell walls. Except in some species or certain tree parts or tissues, lignin is distributed essentially in a uniform pattern across the fiber wall. It is also chemically liked to wood hemicellulose, which further complicates its removal during chemical pulping.

 In its natural state in the wood cell wall, lignin is referred to as "protolignin" or native lignin and is markedly thermoplastic. It is also very it much less hydrophilic than either cellulose or hemicellulose, almost to the point of being hydrophobic. As such, lignin in the pulp fiber has the general effect of inhibiting water absorption and fiber swelling, and can render the fiber less responsive to mechanical refining. However, since lignin is it does possess a characteristic that can be used to advantage in mechanical pulping, where high temperatures soften the lignin.

 The basic structure -of-lignin-differs to some extent between softwoods and hardwoods. In commercial softwoods, the prominent repeating structure is known as a "guaiacyl" unit, which contains a single methoxyl group, on the phenylpropane ring; hardwood-lignin, on the other hand, is a copolymer or mixture of guaiacyl and "syringyl"' lignin, the latter containing two methoxyl groups per phenylpropane nucleus.
The ratio of guaiacyl to syringyl units varies from 4:1 to 1:2 among different hardwoods.

PROPERTIES OF FIBER IMPORTANT TO PAPERMAKER Fiber Length Usually it is a belief that a paper made from a long fiber will give more paper strength than that made form a shorter fiber. However with usage of different kinds of raw materials it is possible to produce good quality papers from even short fibers. Clark established a few empirical relationships between pulp strength and fiber length. Burst factor Breaking length Tear factor = = = K1 L K2 L 0.5 K4 L 1.5

Fiber length also influences the general structure and surface properties of a paper sheet. Although fiber length is an important property of fiber yet it is not considered to be very important as its required according to the specific paper product demand.

Cell Wall Thickness

The importance of the fiber wall on properties of paper hand been recognized for a number of years.

The early wood portions of the growth ring may have fibers with comparatively thin wall and late wood fibers have thick walls. The pulps obtained form wood having thin walled fibers give dense and well bonded sheets, and those from thick wall give bulky sheets with high tearing resistance.
It is apparent that thin walled cells collapse and confirm to other fibers easily to give a dense bonded sheet of paper, due to their high flexibility.

Coarseness or Flexibility
It is very important property of fiber. It depends largely on fiber wall thickness. It can be reported as
Flexibility ratio 1/D. Coarseness: defined as weight in mg. of the fibers needed to give a total length of 100 metres.
STRENGTH TABLE FOR MORPHOLOGICAL FACTORS Trend Tensile and bursting strength rising rising falling rising 0 to + + Tearing strength . ++ 0 to + 0 to + Folding strengt h 0 to + -++ + Sheet density 0 to -++

Fiber length Cell wall thickness late wood fraction rising (tube structure) Cell wall thickness early wood fraction falling (ribbon structure) Ratio fiber length to fiber width

Curling of fibers

rising

--

* Porosity, absorbency, air permeability, bulk have a contrary trend.

STRENGTH TABLE FOR CHEMICAL AND PHYSICO-CHEMICAL FACTORS

Trend

Tensile and bursting strength

rising 0 to +

Tearing strength

Folding strength

Sheet density

Average degree of polymerization (D.P.) D.P. very low

0 to +

0 to +

Hemicellulose content Lignin content Stiffness Water retention value

rising rising* rising**

Optimum +

Optimum Optimum to +

Optimum -++

+ +

* Porosity, absorbency air permeability, bulk have a contrary trend. ** Plasticity, bendability has a contrary trend.

CELLS CREATIVE PROBLEMS DURING PAPERMAKING Vessel elements

These cells are present in all angiospermic plant whether woody or non-woody hardwoods contain vessel volume tends to lower wood density. They range in size from 0.2-1.3 mm. in length and 20-300 m in diameter. In general shorter vessel elements are also wider (hardwoods). The larger vessels are generally more narrower (nonwoods). These vessel elements tend to pull away or pick from the sheet surface during printing. Vessels play an important advantageous role in transport of pulping liquor in wood chips.

Parenchyma
Parenchyma can be axial or ray parenchyma. It is present about less than 10% by volume in softwood whereas can be as high as 50% in non-woods. These cells are normally the site of most inorganics which can be K, Mg, Mn, Ca, Si. Crystallized deposits of these material and amorphous of silica are present in parenchyma cells. These inorganic materials contribute to ash in wood or nonwood. They are problem for some very high purity pulp and promote scale formation in equipments used for recovery of pulping chemicals. Parenchyma cells are also the originators of organic extractives which are undesirable in dissolving grade pulp and cause pitch problem in pulp and paper mills. In absorbent grades of pulps they render the fibers less wet table reducing liquid absorption rate.

Parenchyma cells are some times as small as 10-100 m thus are responsible for giving fines content to pulp causing higher drainage rate of stock.
These cells also contain gums, oils, resins, latex chemicals during pulping. They are very thin walled cells of poor strength so not desirable in sheet and are generally preferred to be screening out e.g. during depithing process.

Epidermal Cells
These cells present in abundance in monocotyledonous pulps. Since epidermis constitute the outer most covering of non-woody plants. It is hydrophobic and contains wax like substance called cut in. In week epidermal cells give strength and protection to internal tissue. These cells are also containing silica, as in case of rice straw. These cells are not easily separated by cooking chemicals and appear in pulp as masses with sharp toothed margins. Epidermal cells also consume more amounts of chemicals; contain siliceous material thus undesirable for pulping.

Hardwoods yield pulp fibers that on average are about to the length and about width of softness fibers. Hardwoods are generally preferred for printing papers where surface smoothness is increased by short fibers. Softwoods fibers are long and coarse thus advantageously used in packaging or high strength papers. Softwoods can yield any type of mechanical pulp as well. Non-woods are having large variety of cell types. Their cell dimensions vary to very large extent from outer part to inner part. They are having very thin walled and low diameter fibers and contain a large percentage of smaller parenchyma cells. Non-woods are not very suitable for mechanical pulp production and are to be blended with other raw materials pulp to give variety of quality papers.

TABLE : Chemical Composition, and Fibre Dimensions of Some Typical Cellulosic Raw Materials Available in India. Lignin % SEED FIBER: Cotton (Gossypium hirsutum) BAST FIBER: Hemp (Cannabis Sativa) SOFTWOOD: Chir (Pinus longifolia) Sikkim Spruce (Picea Spimulosa) Fir (Abies spectablia) HARDWOOD: Rubber wood (Heavia braslliensis) Salai (Boswellia serrata) Mysore gum (Eucalyptus hybrid) 5.2 26.6 28.6 29.2 Ash % <0.1 <0.1 <0.1 Hemicellulose % 2.0 5.5 7.2 12.3 9.7 Gross & Bevan cellulose % 92-97 79.3 53.5 59.7 59.7 Ave. Length mm. 18 22 3.60 2.82 2.66

20.5 27.3 24.7

<0.1 <0.1 <0.1

14.3 13.0 14.1

51.3 50.7 50.6

1.12 0.88 0.73

Grass & REEDS: Sabai grass (Euliopsis Binata) Kana (Saccharum munj) Salia bamboo (Dendrocalamus strictus) Dava bamboo (Bambusa arunoinacea)
AGRICULTURAL RESIDUE: Bagasse (Saccharum officinarum) Rice straw (Orysa sativa) Wheat straw (Triticum sativum) Jute sticks (Corchorus capsularis etc.)

22.0 20.5 27.8 27.0

1-5 1-5

23.9 23.7 15.1 19.6

54.5 58.2 59.9 57.6

2.08 2.06 1.65 2.73

19-21 12-14 16-18 18-20

2-5 10-16 4-7 2-4

26.6 21.0 23.5 18.8

54.9 53.5 51.5 57.6

1.38 1.13 1.10 0.79

RAW MATERIAL PHYSICAL PROPERTIES

RAW MATERIAL MOISTURE Water in the raw material cell wall is held on and between microfibrils at hydrogen-bonding sites. As water is absorbed/adsorbed into the cell walls, the latter expand, giving rise to a gross change in the raw material tissue as a whole. As this bound water is removed from the walls (by drying), the cell walls and raw material tissue shrink. If there is just enough water to completely saturate the cell wall substance and no liquid water is present in the cell lumens, the raw material is said to be at its fiber saturation point (FSP). Here the water is essentially that confined or bound to the wall substance and any microvoids therein. Raw material exhibits its maximum swollen volume at FSP; any gain in moisture content above FSP induces no further changes in raw material dimensions.

When there is sufficient raw material water to cause in accumulation of liquid in the "cell lumens, is said to be "free water" (or capillary-held water") in addition to the bound water. Since this type of water is held in the raw material's void system, gain or loss of free water, causes no raw material swelling or shrinkage, respectively. If all possible cell lumen and intercellular spaces are filled with water, the raw material is at its maximum moisture content". Raw materials with thin-walled cells have a higher void volume (greater lumen volume) than those with mostly thick-walled cells, and hence have a greater maximum MC.

Raw material (and paper) at any MC will eventually achieve an "equilibrium MC" or EMC if exposed to an atmosphere containing water vapor, and the EMC will always be less than FSP. The EMC attained will vary with relative humidity (RH) of the environment, temperature, and drying history of the raw material (or paper), i.e., whether the wood is approaching equilibrium by gaining moisture or by losing moisture. Shows that once raw material tissue has been dried (desorption), the next time it is exposed to water (absorption) it will not gain as much water at the same temperature and RH. In general, raw materials of higher density will have a greater overall volumetric shrinkage or swell, property. For most commercial raw materials, total volumetric changes from green to oven-dry (or vice versa) are normally less than 15% and are approximately equal to the sum of the R and T dimensional changes.

Calculation of moisture content (MC) on a:

Wet Basis % MCw = (W-D)/W x 100

Dry Basis
% MCd = (W-D)/D x 100 Where: W = wet (as-is) wt. of sample D = oven-dry wt. of same sample % oven-dry = % solids = 100-MCw If either of the above formulae is applied to wood with high levels of organic extractives, the MCs so obtained are not accurate relative to wood substance since it is not possible to use the true weight of dry wood substance only.

Relevance to Pulping
Whether raw material is purchased in chip or-log form, the pulp mill is interested in paying for only the weight of the cell wall substance and not the raw material water .

Thus, knowledge of raw material moisture has a direct financial impact on the total cost of pulpwood.
Another situation in which it is important to know how much water is in the raw material is in the determination of the proper ratio of liquor to raw material in the pulping digester. Fresh raw material chips are rarely more than about 40% ovendry (60% MC on green basis), and chips as wet as this, containing water-swollen - cell walls, are more easily pulped by both kraft and sulfite processes than much drier raw material . As softwood chips dry, the interfiber pits become aspirated, sealing off intercellular pathways for free movement of pulping liquor. In hardwood chips the effects of drying may or may not be as noticeable, varying with the extent of "tylosis" formation (which plugs the vessels).

In both raw material types, however, dry cell wall substance is more difficult to penetrate and saturate with pulping liquor than are sufficiently hydrated cell walls. As one might suspect, overly dry raw material necessitates special procedures for liquor penetration. This is of particular importance in sulfite pulping, but a high level of raw material moisture, either natural or introduced at the pulp mill, is also a prerequisite for various mechanical and thermo mechanical processes. While a certain amount of water in wood is an obvious advantage in pulping operations, in some cases it can also be very troublesome. Specifically, in climates where winters are severe, snow and ice in outside chip piles cause chip handling problems.

Frozen bark is also more difficult to remove. A related problem is frozen pulpwood, which causes chipping problems (more energy, knife dulling) and overall inferior chip quality. Chips from frozen raw materials are thinner than normal and are often undersized (pin chips).

The latter pack more tightly and have a tendency to interfere with liquor circulation in the pulping digester.

RAW MATERIAL SPECIFIC GRAVITY

The wood physical property most commonly examined by the pulp technologist in an effort to evaluate overall wood quality is "specific gravity". This parameter is used to give a idea of how much wood fiber or wood substance can be obtained per unit volume of a given type of pulpwood. In addition, the potential behavior of pulp fibers in papermaking or other manufacturing processes and in the final product can often be correlated to wood specific gravity.

Terminology
Specific gravity is defined as the ratio of the weight of a wood sample to the weight of water displaced by that sample. Consequently, specific gravity (SG) is a pure number and has no units. This ratio is often but incorrectly given the units of g/cm3 and is therefore often mistakenly equated to wood "density," which is defined as:
Density = weight of wood substance (g)/volume of wood substance (cm3)

Both SG and density can be used to provide the same practical information. Since both the volume and the weight of raw material usually change with change in moisture content. Common pulp raw materials have a basic specific gravity range of about 0.35-0.65. Raw materials outside this range are considered either light or heavy, respectively, including both temperate and tropical species. Factors such as tree age, tree part, and growth rate will give rise to variability between species, within species, and within the same tree..

Relationship to Raw Material Anatomy

Wood specific gravity, even for extractive-free wood, varies with wood type (hardwood, softwood), species, within species (due to site and geography), and within the same tree.

This variability can be attributed directly to the combined effects of (a) cell wall thickness, (b) cell size, and (c) the number of cells of a given type, as defined by (a) and (b).

Softwoods
The proportion of earlywood and latewood (fibers) within annual growth increments, together with fiber wall thickness, are important variables governing the SG of coniferous pulp woods. Within a given growth increment, SG is greater in the thickerwalled latewood. Earlywood/latewood ratio, as well as the fiber wall thickness of each zone, varies with species, tree age, growing conditions, and imposed forest management practices. The difference in earlywood/latewood morphology is particularly noticeable in woods, such as hard pines, Douglas-fir and larch. Species with gradual earlywood/ latewood transition show less SG difference between earlywood and latewood and, on the average, are lower in overall wood SG.

Pulp fiber coarseness (wt./unit length) in softwoods varies directly with wood SG and has a strong influence on the behavior of resulting paper products.

Hardwoods
In angiosperms, fiber wall thickness is still major determinant of gross wood SG, but the volume of wood occupied by the vessel system (essentially void space) is also important.

Both of these factors, together with fiber cell volume, combine to produce a broader range of SGs between species than exists among softwoods.
Vessel arrangement and fiber/vessel ratios can also vary with tree growth conditions, making general statements and predictions on hardwood quality difficult. This situation is further illustrated in the fact that hardwoods how less consistency than softwoods in trends or changing SG in both the radial and axial directions (e., with tree age and tree height).

Relevance to Pulping
One of the first locations at the pulp mill where wood SG can exert an effect is at the chipper. High, density woods are actually harder, more difficult to chip, and necessitate adjustment in chipper operation maintenance. Excessively hard" Woods also require more energy for chipping a produce more variable chips. These species include the higher SG hardwoods such as maple, oak, hickory, ash, and birch. Lower SG hardwoods, such as aspen and cottonwood, and essentially all coniferous pulp-woods are considered "soft" with respect to their demands for chipping energy. The pulp mill is also concerned with maintaining a prescribed level of production, and the mill manager would like to get the most pulp possible from the chips going into the pulping digesters. Since these units will hold only a certain volume, higher SG wood will produce (at a given pulp yield) a greater weight of pulp per cook. Lower SG wood results in a lower chip bulk density (kg/m3) and reduced digester loading.

These reductions can also be caused by improper chip geometry, but in general, the most influential factor here is wood SG. A change in wood SG can also affect the mills cooking schedule, since a change in wood density (usually meaning a change in fiber wall thickness) must be accommodated for by changes in cook chemistry, time, and / or temperature. For mechanical-type pulps, energy, mill production, and possibly pulp quality can all be affected by significant changes in wood specific gravity.

Since low-coarseness and high-coarseness fibers will usually collapse to a greater or lesser extent, respectively, in the wet state such fibers will process differently during pulp washing, bleaching, and screening operations.
High specific-gravity woods yield stiff, rod-like fibers which drain water more easily (free pulp) than thin-walled and easilycollapsed (less free) fibers from low specific-gravity wood. These two fiber types also respond differently to mechanical refining.

Relevance to Papermaking
Changes in raw material specific gravity also have an influence on the papermaking process and the characteristics of the final product. Such changes are generally less noticeable within and among hardwood species - in comparison to softwoods - although pulp freeness, sheet wet strength, and sheet density can vary noticeably between certain species.

On the case of softwoods, however, a major change in chip SG will noticeably alter paper machine drainage, sheet wet strength, and final sheet density.
Thinner-walled and lower-coarseness fibers drain slower (are less free) but collapse more readily to yield higher wet strength and higher sheet density, changes in wood SG and pulp fiber coarseness can often be traced to changes in wood species or species blends, but even within the same species, chip SG can vary with forest geography, tree age, and/or tree growth rate.

Raw material SG or its counterpart in pulp fiber coarseness is one of the most influential factors controlling the strength and several other physical characteristics of the paper sheet. The statistical technique of multiple analysis used to predict the performance of different raw material sources always reveals the very strong influence of raw material specific gravity and resulting fiber flexibility or collapse. This is true for both softwoods and hardwoods. Paper properties like tensile and burst decrease with increasing fiber coarseness.

Nonpaper uses for raw material pulps, such as in absorbent disposables (diapers and related products), tissues and towels or in nonwoven fabrics, are also strongly dependent on fiber characteristics related to raw material specific gravity.
Raw material s of higher fiber coarseness will produce bulkier, usually more absorbent, disposables.

RAW MATERIAL STRENGTH The ability of wood to resist tensile, compressive, and shear forces under various circumstances is probably of little direct technical interest to the pulp converter or papermaker.

General Nature
When subjected to an imposed mechanical stress (force per unit area), wood tissue will deform or undergo a certain level of strain (deformation per unit area or dimension). For small strains of short duration, wood is "elastic"; that is, strain is proportional to stress, and the strain is fully recovered if the time of application is short. On the other hand, large strains and/or extended times of stress application can lead to unrecoverable or "plastic" deformation, or to eventual wood failure. This situation is depicted graphically, which illustrates a stress/strain (/) curve for wood strained beyond its "proportional limit" (where and are no longer linearly related). Over the linear range of deformation, the / ratio is called the modulus of elasticity", MOE, or Young's modulus for tensile or compressive stresses. "When measured at constant thickness or at constant weight/area, the term "extensional stiffness" is also used. Stiffness is a term important to both the wood products and the paper industry.

Moisture Effect
Since water swells wood and has the general of separating the cell wall substance on a molecular level, it is logical that an increase in moisture (up to its fiber saturation point), causes a corresponding reduction in measured strength. As wood gains moisture, less is needed to induce a given strain other factors held constant. On the other hand, as wood dries over the moisture content range below FSP, more energy is required to strain the wood, including tensile, compressive, and shear forces.

Temperature Effect
This effect is not simply described due to an interaction with wood moisture. Generally speaking, raw material strength is reduced by increasing temperature at a given level of raw material moisture, and below FSP, higher moisture content at a given temperature usually means weaker raw material . Interactions between -temp time, and pH of the system will determine the overall effect on raw material strength.

For raw material treated to high temperature (150oC and up) while in water, hydrolysis of the carbohydrate fraction takes place, and the raw material can be weakened substantially.

Hardwoods are more affected by this type of treatment than softwoods.

At elevated temperature and in the wet state, major wood components become thermoplastic or soften over different ranges of temperature - hemicelluloses: 50-60oC; lignin: 90100oC; and cellulose: 230-250oC. Importance to the producer of thermo mechanical pulps, lignin in dry wood must be heated too much higher temperatures (130-190oC) before it becomes thermoplastic. At ambient temperature and moisture content, raw material becomes weaker with age (time) due to very gradual hydrolysis of the cellulose. Since this is an extremely slow process, such degradation is normally of no consequence to the pulpwood user.

Specific Gravity Effect

If one considers the factors that control wood SG, it is easily seen why it has a strong influence on wood mechanics at any level of wood moisture and temperature. For the various tree species used for pulp, a given wood strength property, S, is related to SG by the equation, S = k (SG)n, where n and k are constants. Thus, wood chemistry, anatomy, and ultra structure at a given temperature and moisture content all combine to produce differences in the strength behavior of different wood sources.

Relevance to Pulping
Raw material strength, as reflected in the factors of hardness and rigidity, determines the mechanical behavior of the composite raw material matrix and its resistance to imposed stresses, thereby determining the ease with which raw material is processed in the aforementioned operations. The raw material strengths probably of most concern to the pulp mill are compressive and shear strengths (mostly parallel to grain or tree axis) that must be overcome for chipping and chip refining. The energy needed here to cut and fiberize can be a significant portion of the total cost of pulp production, particularly those operations that rely to a large extent mechanical energies.