Starch

What is Starch Starch is a natural carbohydrate polymer. The molecular formulae of starch is (C6H10O5)n. Mainly starch is used in paper mill to improve dry strength and surface. Its molecular weight is very high. Native starch has a very high viscosity. On the other hand modified starch has lower viscosity. The main sources of starches are regular corn, tapioca, waxy maize, wheat and potato. After cellulose fiber and mineral filler, starch is the third most widespread raw material in paper mill industries. Molecular weight of starch is a factor for application of starch in paper mill industries. The maximum molecular weight (non-degraded) of starch is suitable for wet-end application. Because the non-degraded starches have huge dimensions, so the binding power is increased. On the other hand, reduced molecular weight (degraded) starches is suitable for surface application. This is the reason that degraded starches have lower viscosity. Generally the starch is used in paper mill in three different stages for different function. The stages are wet end section for internal sizing, size press for surface sizing, and size press or offmachine application for coating. The most common wet-end starches are cationic starches or amphoteric starches or native starches while the surface starches are oxidized or hydroxyethylated. Types of starches Mainly starch is classified into two types. Native starch and modified starch. Native starch: The most common native starches are corn starch, tapioca starch, waxy maize starch, potato starch, wheat starch and rice starch. Modified starch: Cationic starch, amphoteric starch, oxidized starch etc. Function of starches:

Starch enhances the stiffness and bonding of paper sheet. Improve formation improve internal bond, Improve surface strength and wax-pick Increase tensile strength Improve fiber fines, filler and chemical retention. Improve drainage. increase dry strength properties better writing and printing surface reduce linting and dusting Reduce cost, because it is allowed to use more filler and more recycled fibers. Increase runnability and productivity. As breaks are lower. Energy consumption lower due to high binding power.

Maize starch
Maize starch is also known as corn starch. Maize starch is most popular among the native starch. It contains low ash and low protein. In paper mill industries maize starch or corn starch used as wet end additives, tub sizing or surface sizing agent, coating agent and binder. Maize Starch is changed into a smooth paste during cooking within a short time. Function of maize starch In paper mill industries the primary function of corn starch or maize starch is increase dry strength and surface improvement of paper. As a wet end additives maize starch increase paper strength, increase paper stiffness and rattle of the paper. As a surface sizing agent it is improve appearance and erasibility, restrains ink penetration, form firm surface (which is suitable for better writing and printing) and also prepare the paper sheet for subsequent coating. As a Coating agent maize starch enhances printability and gives a glossy and a fine surface of the paper. Since the pH value of maize starch paste is sustained in neutral range or below the neutral range so it is unnecessary to add any antifoaming agent into the maize starch systems because foaming is normally related with high pH. Moreover maize starch does not rupture during cooking whereas tapioca starches split up.

Specification of Maize starch 1. Appearance: white or light yellow shadow 2. Fineness (100 mesh): 99.5% min 3. Moisture content % w/w (at 105C-110C): 14max 4. pH value: 4.5-6.5 5. Whiteness: 90.10 min 6. Protein: 0.50% max. 7. Ash content % w/w (at 550C): 0.3 max. 8. Cold water solubility: Nil 9. Fat: max. 0.20% 10. Adhesivity: good 11. Shelf Life: 1-2years 12. SO2: max 30mg/kg

Cationic starch
Cationic starch is a modified starch. The cationic starches mainly used as wet-end starch. Although native starch can be used as wet-end starch, but cationic starches are more preferable. As the cationic starches are positively charged, they are easily attracted by the negatively charged cellulose fiber and fillers. As a result fiber-to-fiber and fiber-to-filler bond are increased. Hence improved the retention of fines and filler and also increased paper sheet strength. Commercially Available cationic starches are two types; quaternary ammonium type cationic starch and tertiary amino type cationic starch. Quaternary ammonium type starch is cationic in all pH range, whereas tertiary amino type starch is cationic only in the acidic range. It is the main problem of the application of tertiary amino type of cationic starch. Hence the applications of tertiary amino type of cationic starch are limited. The quaternary ammonium containing group attached at the C6 position of the starch. Since the OH group of this position is more active. Benefit of Cationic Starch in Paper mill Industry: Cationic starch enhances paper strength, water drainage, retention, improve paper quality; reduced dusting, linting and size addition; greater control of paper making process hence less paper web breaks and improve paper machine runnability as well as productivity. Cationic starch also allowed using more filler and more recycled fibers so reduce furnishes cost. As a surface size agent, cationic starch improves stiffness, opacity, printing quality and brightness.

Specification Of cationic starch 1. 2. 3. 4. 5. 6. 7. Physical state: odorless powder Moisture Content % w/w (at 105C-110C): 14 max pH value: 10% solution, 5-8 Viscosity 5% at 50: high (greater than 2200 cps) Whiteness: 88% min. Fineness (100 mesh): 99% min Nitrogen content: up to 0.3%

Tapioca starch
Tapioca starch is a native starch. The starches which are produce in Tropical countries-such as Brazil, Nigeria, Indonesia, West Africa and Thailand are called tapioca starches. The most common tapioca starch is Cassava starch. Other tapioca starches are arrowroot, sweet potato, taro, sago, and yam. The properties of Cassava starch are highly desirable for paper-making. The benefits of cassava starch are following:

Low price Low dirt Whiteness is high Processes better water holding properties High viscosity Form clear paste and strong film

Application of cassava starch: Cassava starch is widely used at wet end additives. Moreover it is also used as a tub size, surface size, beater size and surface coating in the paper mill industries. Specifications of cassava starch 1. 2. 3. 4. 5. 6. 7. 8. 9. Appearance: white Moisture content at 105C-110C %w/w: 14max. Adhesivity: Good pH value: 10% solution, 5-8 Viscosity 5% at 50: high (greater than 2200cps) Nitrogen Content: 0.3% Min Solubility: rapidly and completely after batch or continuous cooking Toxicity: No health hazard during normal handling Shelf Life: more than 12 months (under normal storage and undamaged state).

Genetically Modified Starch Modified starch should not be confused with genetically modified starch. Which refers to starch from genetically engineered plants, which have been genetically modified to produce novel carbohydrates which might not naturally occur in the plant species being harvested. The modification in this sense refers to the genetic engineering of the plant DNA, and not the later processing or treatment of the starch or starch granules. Genetically modified starch is of interest in the manufacture of biodegradable polymers and non-cellulose feedstock in the paper industry as well as the creation of new food additives. Sukhjit has a diverse portfolio of Modified starches suitable for various applications:these products have been highlighted below. Spray Starch (Sukhspray) Sukhspray is a speciality starch for spray application which can be used to improve the dry strength properties of Kraft paper. Pre-Gel Starch Pre- gelatinized starch is used to thicken instant desserts, allowing the food to thicken with the addition of cold water or milk. Similarly, cheese sauce granules (such as in Macaroni and Cheese or lasagne) or gravy granules or sauces may be thickened with boiling water without the product going lumpy. Commercial pizza toppings containing pre-gel starch will thicken when heated in the over, keeping them on top of the pizza, and become runny when cooled. Apart from food pregel starch find use in Textile & Laundry Applications due to its properties of cold water solubility &good water absorption capabilities. Cationic Starch (Sukhcat) Cationic starch is produced by treating the slurry of partially swollen granules of starch with a reactive compound. This reagent contains quaternary nitrogen, yielding a positive charge that is independent of PH. The reagent usually attaches to the starch at the C6 position, the most accessible of the OH groups. the typical level of derivatization is one to two charged groups per hundred glucose units. Because the reaction is usually carried out in slurry, it is expected that the distribution of charged groups will be highly non- uniform. Cationic Starch finds extensive use in the paper industry and its key functions are as a Dry strength additive, Emulsification of sizing efficiency at lower alum level, which ultimately helps to reduce linting problem of paper.

Yellow Dextrin Yellow dextrin is manufactured by partially hydrolyzing Starch, using the dry roasting method in the presence of a catalyst: The dextrinisation chemically reduces the starch molecules into smaller components. Yellow dextrin has low viscosity and is very sticky and hygroscopic in nature. Used in the foundry as a binder for cores. Yellow dextrin helps in increasing dry strength at the same time being completely soluble in water. This product also finds its application as a binder for mould and core washes. Its binding abilities make it an essential ingredient in various other applications, such as Adhesives, Gums, Pastes Pyrotechnics. White Dextrin White dextrin is manufactured by partially hydrolyzing starch, using of a catalyst. The dextrinisation chemically reduces the starch molecules into smaller components. White dextrin is white in colour but with reduced viscosities. its cold water solubilitys rang from 25% to 65% White dextrin produce;s a light colour ed paste that set to soft but a definite gel. The higher solubility white dextrin Can be used at much higher concentration to yield very soft gels. Its solution is a half transparent plaster. White dextrin has good glutinosity and resolution. It as an indispensable excepiant for medicine food and health care industry. It is also used as an additive in the certain applications for the manufacture of Textile, Adhesive and Dyes. Oxidised Starch (sukhsize) Native starch is treated with a variety of oxidizing agents and oxidized starch as are obtained. oxidized starches have shorter chain lengths than native starches. It improves whiteness and reduces microbiological content. In addition, the hydrogen bonding reduces the tendency to retro-gradation. Producing soft- bodied gels of high clarity, oxidized starches are the best thickener for applications requiring gels of low rigidity. This improves adhesion in batters and breading. Diluted solutions of highly oxidized starches remain clear on prolonged storage, making them suitable for clear, canned soups and transparent confectionery products. oxidized starch is also widely used in surface sizing for paper industry and for warp sizing in textile industry. Lamination, paper conating, paper Adhesive Building materials. Thin Boiling Starch Thin boiling starch has low and uniform viscosity, which does not change much with temperature unlike native starches which show wide variation in viscosity. Thin boiling starches are manufactured by acid addition to native starch slurry. Low viscosity enables its use in high concentrations without the viscosity getting too high. In some applications, for example in instant soups, thin without any specific technical function. Thin boiling starch non congealing characteristic, transparency of past and lower viscosity ensure easy working compared to other modified starches. Unlike gum and glues which require soaking, thin boiling starch is readily

dispersed in water and can be boiled into a smooth paste without any pretreatment. Its application in yarn weaving is particularly advantageous as it does not develop abrasive points on over drying and its flexible film gives the yarn the desired elasticity. Modified Starch Modified starch is an additive prepared by treating starch or starch granules, causing the starch to be partially degraded. Modified starch is used as a thickening agent, stabilizer, or an emulsifier. Apart from food products, modified starch also find use in paper manufacturing, Pharmaceuticals and various other industrial applications. Starches are modified to increase their stability against excessive heart, acid, and freezing to change their texture or to lengthen or shorten gelatinization time. Amodified starch may be an instant starch which thickens and gels without heat, or a cookup starch. While Acid-treated starch is prepared by treating starch or starch granules with inorganic acids. Other treatments may produce modified starch with different enzymes, such as alkaline- modifierent starch Bleached Starch Oxidized starch Enzyme-Treated starch oxidized starch, Enzyme, Treated starch Acetylated starch and Acetylated Oxidized starch.

Article (Research & Development)

Starch : An Important Component of the Paper Making Process

Date: July 2009

Introduction

To most people, starch is viewed as a major nutritional material to provide energy for human or as a major functional ingredient in food recipes to provide characteristic viscosity, texture, mouth-feel and consistency of many food products. However, in fact, starch has found uses in various nonfood applications such as paper, textile, cosmetic and pharmaceutical industries. Paper industry is one of the largest users of starch. Starch is, in fact, the third most prevalent raw material component in paper, only surpassed by cellulose fiber and mineral filler. Depending on the type of paper produced, starch content in the final products may be as high as 10% by paper weight. Starch used in paper manufacture is generally found in three application areas which are wet end internal sizing, surface sizing and coating.
Papermaking process

The general components of paper machine are illustrated in Figure 1. In the paper making process, a dilute suspension of fiber (0.5-1%) and chemicals are pumped to the head box which feeds the fiber suspension evenly onto the moving wire conveyor belt. Large amount of water is drawn away as the fiber suspension moves along with the wire conveyor belt. At the end of the wire section, a moist sheet of paper is formed. It is then passes through a series of pressing cylinders where more moisture is removed. The remaining water in the paper sheet is further removed in the drying section where the sheet is passed over a large number of steam-heated drying cylinders. At this point, the sheet is almost completely dry. Way down in the drying section is the size press where a starch paste can be applied on the paper sheet to improve surface properties. Following the size press, the sheet is dried again. If coated papers are produced, the pigment coating may be applied at this point. In some cases, the coating may be performed on an off-machine coater (not integral to the paper machine). The paper is then passed through a vertical series of hot polished iron rollers (called calenders) to smooth and polish the surface. The paper sheet is finally wound onto reels for further processing if desired.

Starch application in papermaking process

Starch can be employed during papermaking process in three main areas: 1. Wet end refers to the portion of the process which contains cellulosic pulp fiber and other small particle components (such as cellulosic fine, fillers, etc.) dispersed in a large volume of water. Starch is commonly added in the wet end of the paper machine to serve as a retention and dewatering aid. Although native starch can be used, cationic starches have been preferred wet-end starch additives. By being positively charged, they are attracted to the negatively charged cellulose fiber and the negatively charged fillers. This increases fiber-to-fiber and fiber-to-filler bonding; thus, promoting a high degree of filler retention as well as strength increases at low application levels compared with native starch (Lawton, 2000). The cationic starches that are commercially available are the tertiary amino or the quaternary ammonium derivatives. While the quaternary ammonium starches carry a cationic load in all pH ranges, the tertiary amino starches are only cationic in the acid range. Therefore their possibilities of application are limited. As a result of the progressive conversion from an acid to an alkaline operation in the manufacture of paper and the increased use of calcium carbonate in the wet end system, the use of tertiary amino starches is diminishing (Hellwig et al., 1992). 2. Surface sizing In the paper industry, the largest volume of starch is used for surface sizing. Surface sizing is an operation in which paper runs through a sizing solution and then through sizing rolls. These rolls press the sizing into the paper and remove the excess from the surface of the paper. The main purpose of surface sizing is to improve surface properties, to give a better writing and printing surface and to minimize linting. The concentration of starch in a sizing solution can range from 2 to about 15% depending on the type of size press machine and product requirements (Maurer, 2001). Cooked unmodified starch is too high in viscosity for most sizing operation; thus the viscosity of the starch paste is usually reduced. This can be done at the paper mill by either enzyme or thermochemical conversion. However, these depolymerized starches have tendency to retrograde or reassociate resulting in a less sizing performance. Alternatively, preconverted or modified starches may be obtained from the starch manufacturers. Oxidized starch is one of the most common modified starches for use in surface sizing because of its good film forming characteristic and reduced tendency to retrogradation. However, when the paper is recycled, oxidized starch which contains negative charge can act as a dispersant and contribute to the loss of filler and the starch itself to the waste water causing pollution problem. Substituted starches such as acetylated starch, hydroxyethylated starch and cationic starch are gaining popularity in surface sizing operation. Beside their benefits of reduced retrogradation, these starches do not cause filler dispersion if the paper is repulped in the recycled process system. 3. Paper coating In paper coating, a layer of pigment, adhesive and other supplementary materials is applied to the surface of paper. Coating provides whiteness, brightness, gloss and opacity to the paper as well as a smoother and more uniform surface. Pigment is the primary material for coating paper. The most commonly used pigments are clay, calcium carbonate, titanium dioxide and talc. In paper coating operation, starch is used as an adhesive or binder to bind the pigment particles to each other and to the paper. Starches

used for surface sizing as described above can be used as coating binder as well. However, coating starches need to have lower viscosities than starched used in other segments in the paper industry. This is because there is a need for the presence of high amount of starch in coating formula to provide strong binding for the pigment and at the same time the coating should still be leveled and applied as a film on the paper surface. As previously mentioned in surface sizing section, the negative charge of oxidized starch could contribute to the loss of pigment filler if the finished paper is repulped; thus, the popularity of oxidized starch as a coating binder has been declined. Hydroxyethylated starch is considered one of the best materials for use as coating binders due to its excellent film forming properties and strong resistance to retrogradation. However, higher cost usually limits its use in the conventional coatings.
The future of starch in the paper industry

Although the consumption of starch by the paper industry is presently high, many synthetic materials are available that can substitute for starch. With an increasing demand for higher paper properties and rapid advancements in papermaking technology, these synthetic substitutes are often preferred especially for the production of high grade paper due to their higher performance. Currently this challenge can be met by many advantages that starch has to offer. Starch is an inexpensive raw material obtained from a renewable resource. It is a natural polymer with high molecular weight that can be chemically or physically modified to adjust its rheological characteristics and to provide a specific performance. Furthermore there is a current global trend on consumer consciousness to protect world environment which discourages the use of synthetic materials in many applications and promotes their replacement by natural organic compounds. This environmental trend is opening up new product opportunities for starch in the paper industry. For example, starch-based pigments have recently been developed from starch acetate nanoparticles (Figure 2) to replace the mineral pigment filler (Karvinen et al., 2007). Starchgraft-copolymer has been developed to produce new materials with properties that combine the advantages of natural and synthetic polymers (Maurer and Kearney, 1998). With a continuing progress in modification technology, the development of new materials from starch with specialty characteristics seems to be unlimited. As a result, the potential of starch as an important raw material in the paper industry remains promising both at present and in the future.