Say ___ ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY voLume 18 ila Sl FOURTH EDITION eva Picment DisPERSIONSCONTENT INDEX (vol 18) (with hyperlinks) Eclited by hp tcherwer are PAPER PAPERMAKING ADDITIVES PATENTS AND TRADE SECRETS PATENTS, LITERATURE PERCHLORIC ACID AND PERCHLORATES PERFUMES PEROXIDES AND PEROXIDE COMPOUNDS ~ INORGANIC PEROXIDES - _ORGANIC PEROXIDES PESTICIDES PETROLEUM = NOMENCLATURE IN THE PETROLEUM INDUSTRY - ORIGIN OF PETROLEUM = COMPOSITION - DRILLING FLUIDS = ENHANCED OIL RECOVERY - REFINERY PROCESSES, SURVEY - PETROLEUM RESOURCES, PHARMACEUTICALS. PHARMACEUTICALS, CHIRAL PHARMACODYNAMICS PHENOL PHENOLIC RESINS PHOSGENE PHOSPHINE AND ITS DERIVATIVES PHOSPHORIC ACIDS AND PHOSPHATES. PHOSPHORUS, PHOSPHORUS COMPOUNDS PHOTOCHEMICAL TECHNOLOGY - SURVEY - _PHOTOCATALYSIS PHOTOCONDUCTIVE POLYMERS PHOTODETECTORS PHOTOGRAPHY PHOTOVOLTAIC CELLS PHTHALIC ACIDS AND OTHER BENZENEPOLYCARBOXYLIC ACIDS PHTHALOCYANINE COMPOUNDS PIGMENT DISPERSIONS 15 25 42 64 7 89 101 141 158 158 161 164 174 188 200 217 223 237 267 286 292 311 317 323 347 356 387 388 398 407 419 440 466 478 504 511PAPER Vol 18, PAPER Papec consists of sheet materials that are comprised of bonded small discrete fibers, The flbers usualy ae cellulosic in nature and are held together by Inydeogen bonds (se Cz.cse, The fibers are foomed into ashect on fine screen froma dite watersnspension. The word paper is dexived fro ‘apy, a sheet made ia ancient times by pressing together very thin stipe of an Egyptian seed (Cio papi) (1). ‘Theeuly use of papce was 282 wating acdinm which seplaced day tablets, stone, pazchment, and papyaus sheets. apyas sheets ate aot considered papec because the individual vegetable fibers ae aot separated and hen seformed ito the shet, Paper appatetly oxginated in China in 108 2 snd was ade feom fax and hemp of back fiboes of certain tes 2). The manufactte of paper from bask and bamboo speead feom China to Japan where fas manufsceue begun inca 610. Papesinakng from Bax and hemp spread theough Centeal Ass, the Middle East, and eventually ito Eucope. Spain and Italy were the eady European papermaking centers. "The fist European paper was aude in Spain i 1150, in Feance by 1189, ia Germany by 1520, and in England by 1494. Papeemaking wat itzoduced inthe United States in ea 1700 by Wallan Rittenhouse ia Philadephia; a history of US. papermaking i avaiable 3). Papers made ina wide vasety of types and grades to serve many functions, Weing and pining papers constimte ca 30% of the total production “The balance, oxewpt foe tave and toweling, used primardy for packaging (qy). Papechoaed differs Grom paper Jess lei than conventional pape: “More thas 95% of the Base mater sed in paper and board manufacte (4) is ibrous, Whereas alge (50%) percentage originates from wood (0), the filer contents of some grades of paper approach SP Many tee species encompassing hoth hardwood and softwood are sed to prodce pulp In addition tothe lage numberof wood types, there ate many different mantfscturing process involved in the conversion of wood to pulp. These rage from mechanial processes, by which only mechanical eneggy i used to separite the fiber fiom the wood mattis, to chemical processes, by which the bonding mater, ligni (q), is removed chemical, Many combinations of mechanical and chemical methods sso are employed (ce Pu), Pulp properties ate detesmined by the raw material and manufictusing process, and must be matched tothe aceds of the final paper product. In mechanical plps, the fers ace sepaested by mechanical enegy, Because thete is ao chemical removal of wood components, the process ceslts ins high (05%) pup yl. The chemical composition of mechanical pulps is simile to those of native wood ie they contain significant amounts of ign ‘nd hesncelulose (qv) ia addition to the base cllalose component ofthe fiber. Inthe stone grouadwood process, bess ate sepusated fom the wood by ining logs against sevolving stone wheels, The resultant fiber ave factused and much Bbdlar debs x generated. These pulps ace used wheve opacity and good printabdiy ae needed. The presence of lige amouits of ligni, however, celts ia lower inteibes honding and tensile staength, aad poor ight stability. Such pulps ae bleached with sequences that mata high palp yield and do not eemove lignin. Typiea bleaching chemicals ae ethoe alkaline Ihydoogen peroxide or sodium hydoslite (dithionite). Brightness levels oF BM usally can be achieved. "Newer methods of mechanical pulp production invalve disk refines to produce pulp foun wood chips, Chips ate paned between clotely spaced evolving disks and the fee i broken fie foun the wood mutex. The pulps generally conta les debs and longer fess than stone groundwood pulp. Retiner mechanical pulp (RMP) is produced at atmospheric pressuse from a disk efi 1 themomechanical plp (IMP) process chips ate steamed at 120°C privet fibesization ina pressutzed disk eines. Compatcd to stone groundwood pulp, TMP is comprise of longer, lest damaged fibets and lees debas, which eeults in improved stengsh but some opacity oes, Theemomechanical pups can be used to educe or eliminate chemical pulps in many blends, Softwood isthe prefered exw mates to prodhice optimum strength in the product Certs chemical treatinents can be employed dusig the TMP process to achieve improved strength Sodiam allie and hydeogen pesosie have tase used ether for chip pee- or post-teeatment ofthe TMP pulp; such pulp is called chenihermomechanial pulp (CTMP), The strangth improvement, ‘which may be 50%, ane obtsined at some satfce toyed and opacity. The yes of mechanical pulps ate 90-95" at it gpeily ie thicker,henviee, nd itis the oldest ofthe refiner processes In Athelovser yields ace associated with hema teat [No principal commercial pips ate prodaced in the next lower cll range, i, 80-P “The next significant cass of pulps, semichemical polps, generale chaesctrized bya yield of less than 80% significant amounts of material ae removed by chemical action, Semichemical plps are produced by mild chemical digestion of chips prior to reduction o pp in a dik refines. Vids ane 70-80% and the pulp contains lower inthe wood from which s was derived, The main use for this product sin comigated med, in which the stiflaess resulting from the lignin and hemiedlulose components a product advantage. Hardwoods wually age the bse g from the lack of a suitable Iemielolse content woods for sn henna pulps Use af the neutal aulite process declining be secoveryapstein, Newer processes, which ate based on sodium carhonate-sodium sulfide, ie the gseen iquor process, or sodium hydroxide-sodiuan carbonate, a eplaciag the acuta suite sequeace. Compared tothe neue sulfite pulp, these laine semicheaial pulps age daskeeia color nd have slightly highes lignin contents Chemical pulps have greatly ceduced lin and hemicllulose contents compazed tothe native Wood, 8 these components are dissolved dosing henna digestion, Because the ign is resnaved, nich less mechanical energy ie needed to separate the fers from the wood mati, and the sulting pip fibers are undamaged and strong, Chemical pufps ave used The principal process for producing chemical pulps is the kat process mixtures of sodium sulfide and sodium hydeoxide are the pulping, chemical, and yields ate 46-56%, The higher yield pulps cootain about 10% lignin, They ase used in bags or linerboard where steength i important. The lower yield pulps epialy ae Bleached to remove vill all lignin and to produce high bightaess (W%+), These pulps are used where permanence and whiteness axe nceded in addition to strength, Bleaching i a multistage process. Hementlchlosiae was commonly used asa Mesching agent (ee Bezicias Aces, rut asc aren, but the environmental impact of eluents from chlorine Meacheres which contained dioxins led to replacement by cloxine oxide (see Crncns oxscioacis ao 5). Tn onder o conte! the formation of diosins, dheze as been a eend toward extended cooking and/or ‘oxygen daligaitication, followed by close dioxide using oxygen ugmeatation of extraction stages ox occasionally oxygen and peroxide augmentation, “The use of oxygen compounds, eg, gaseous oxygen, ozone (qs), and hydrogen pecoxide (qs), it becoming more important tl pooblems rea incipally for strength and peefoemance in a vader ofp ad paperboned poo ducts, Reclaimed fiber accounts forca4% of the total fiber used in the United States. variety af sequences are used to disperse and dean the waste {ihee. Emphasis is on mechanialscrening and cleming, washing, and flotation. The properties ofthese pulps depend largely on the input rie materia sind geoenlyarlower in strength and brightness than a compatable virgin pulp, Typical yields for de-inking processes range From 60 to 8 [Nomwood fibers tensed in elatively smal volumes. Examples of nonwood pps and prodicts include cotton liners for writing paper and fiers, bagasse for cornagted media, part for filler paper, or Mana hemp for tea bags. Synthetic pulps which are based on sch materi a las (x) and polyolefins also ae use (ee Otsrov roc). These pulps ate relatively expensive and usually ae used in blends with wood pulps where they contibute a ropety such as tear cesistance, stiffness, or wet stiegth whichis aceded to mect a specific produc requirement Physical Properties Most propesis of papes depend on direction, ie, the machine ctossnachine, and thickness directions. For example, strength is preter if messuced inthe machine direction ie the diecton of manuficeue, than in the croxs-machine diecton. For paper made on a Fourdinice paper machine, the rio ofthe ‘sco values vices fiom about 1.5 to 25, An even geste anisotropy is obseaved if either ofthe in-plane values x compaded to the out-of plane steeagth pecs quite weakin the thickness direction; it may be considered an orhotropic mate, e, one possessing theee morualy pespendiclar symmetry planes (5). There ae seven reasons fox this anisotropy: Wood pulp fibers ate long, sleades, and usualy sibbon-like after papee formation, rather than igclas in eos section, Dusing the deposition ofthe suey onto the wie, the fibers tend 0 lie inthe dizecton ofthe moving wire, and the extent to ‘which they do this depends lagey on the ratio ofthe jet and wiv speeds. The sheet teads to become stronger in the machine dzection a8 mote fibers ine up inthe sume dzection. Another important factor i the tendency for paper to become stionger ifs deed under rests, prevented from sinking Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition) 1