ࡱ; vtrpnljhf ~ | z v   !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrstuwxyz{|}~Root Entry Fh@CompObjbWordDocumentkObjectPool]W]W  FMicrosoft Word 6.0 Document MSWordDocWord.Document.6;  Oh+'0l   ( Lp  $HC:\WINWORD\JELDOK.DOTZdravko Ra[kajUprava za informatiku@/@@ܥe= ekLLQQQQD,W,W,W,W,W0\WW,WXj[ gLhghghghg&gggggghi:jjTIkLXjQg hghgggXjgQQhg[ggggQhgQhggQ SjQQQQggg)gSVEUILITE U ZAGREBU UMARSKI FAKULTET DRVNOTEHNOLOKI ODSJEK fillin "Type the title of the dissertation (for example, A Study of Corn Futures on the Commodities Exchange)." \* upper UTJECAJ TEMPERATURE NA SORPCIJSKA SVOJSTVA BJELJIKE I SRI JELOVINE DOKTORSKA DISERTACIJA Mr. sci. Jelena Trajkovi, dipl. in.fillin "Type the department name and committee name if applicable (for example, Department of Economics)." \* upper fillin "Type the location of the university; include city and state (for example, Chicago, Illinois). Text will be converted to uppercase." \* upper RUJAN, 1997. SADRAJ SADRAJ .......................................................I POPIS TABLICA ...........................................III POPIS SLIKA .............................................. V TUMA OZNAKA ........................................... VII TOC \o "1-3"1. UVOD I POSTAVKA PROBLEMA 1 2. OPI DIO 4 2.1. SR I OSRAVANJE 4 2.1.1. Prijelazna zona 7 2.1.2. Vlanost 8 2.1.3. Blokiranje provodnih putova 11 2.1.4. Sazrijevanje radijalnog parenhima 12 2.1.5. Biokemijske promjene 13 2.1.6. Ultrastrukturne i citoloke promjene 15 2.1.7. Evolucijski pogledi na osravanje 16 2.2. RAZLIKE IZMEU BJELJIKE I SRI; OSVRT NA JELU 19 2.2.1. Kemijske razlike 19 2.2.2. Razlike u fizikalnim svojstvima 21 2.3. HIGROSKOPNOST, SORPCIJA I RAVNOTENA VLAGA S OBZIROM NA OSRAVANJE 23 2.4. UTJECAJ TEMPERATURE NA SVOJSTVA DRVA 27 2.4.1. Kemijske promjene 27 2.4.2. Strukturne i morfoloke promjene 35 2.4.3. Dimenzijska stabilizacija 37 2.4.4. Promjena boje 41 2.5. MIKROSKOPSKA, KEMIJSKA I FIZIKALNA SVOJSTVA JELOVINE OPENITO 42 2.5.1. Mikroskopska graa jelovine 42 2.5.2. Kemijska graa 43 2.5.3. Fizikalna svojstva 43 3. MATERIJAL I METODE 44 3.1. PRIPREMA MATERIJALA 44 3.2. METODE 44 3.2.1. Higroskopnost i stabilnost 46 TOC \o "1-3"4. REZULTATI I DISKUSIJA 50 4.1. HIGROSKOPNOST 50 4.3. STABILNOST 55 5. ZAKLJUCI 66 6. SAETAK 67 7. SUMMARY 68 8. ZAHVALA 69 7. LITERATURA 70  POPIS TABLICA TOC \o "8-8"Tablica 2.1.1. Nazivi bjeljike i sri u razliitim jezicima (poljari, 1969) 4 Tablica 2.1.2. Proces starenja u kambiju i ksilemu (Bosshard 1974) 6 Tablica 2.1.3. Nazivi razliitih tipova osravanja u razliitim jezicima (Bosshard, 1966) 7 Tablica 2.3.1. Usporedna tablica udjela ekstraktiva i sorpcijskih svojstava nekih vrsta drva (prema Wangaardu i sur., 1967. te Gorieku, 1992) 26 Tablica 2.4.1. Temperature omekanja glavnih sastojaka drva u suhom i vlanom stanju (Goring, 1963, prema Hillisu, 1975) 32 Tablica 2.4.2. Svojstva bubrenja i sorpcijska svojstva toplinski obraene bjeljike borovine (Pinus sylvestris) (Kollmann i Schneider, 1964) 40 Tablica 2.5.1. Udjeli kemijskih sastojaka u drvu jele (Abies alba) i bora (Pinus sylvestris) (prema Wagenfhr, Scheiber, 1974; 1Fengel i Ludwig, 1989; 2Shortle i Bauch, 1986; 3Fengel i Grosser, 1975). 43 Tablica 3.2.1. Mjerila za ocjenjivanje stabilnosti drva (Noack, Schwab i Bartz 1973) 49 TOC \o "8-8"Tablica 4.1.1. Masa parene i neparene bjeljike i sri jelovine, T-test 51 Tablica 4.1.2. T-test ravnotenog sadraja vode za uzorke u paru pri 65%-tnoj relativnoj vlazi zraka. 52 Tablica 4.1.3. T-test ravnotenog sadraja vode za uzorke u paru pri 86%-tnoj relativnoj vlazi zraka. 53 Tablica 4.1.4. T-test ravnotenog sadraja vode za uzorke u paru pri 34%-tnoj relativnoj vlazi zraka. 54 Tablica 4.1.5. Svojstva sorpcije i bubrenja bjeljike i sri parene i neparene jelovine 55 Tablica 4.1.6. Utezanje u kvazilinearnom podruju (od j=86 % do j=34 %), utezanje zbog suenja te apsolutno utezanje 57 Tablica 4.1.7. Neparena bjeljika 58 Tablica 4.1.8. Neparena sr 60 Tablica 4.1.9. Bjeljika parena 72 sata na 105 C 62 Tablica 4.1.10. Sr parena 72 sata na 105 C 64   POPIS SLIKA TOC \o "7-7"Slika 2.1.1. Popreni presjek svjee posjeenog stabla jele (Abies alba Mill.) 3 Slika 2.1.2. Raspored sadraja vode po poprenom presjeku jele nakon ruenja (Sinkovi, 1994) 9 Slika 2.1.3. Popreni presjek svjee posjeenog stabla jele (Abies alba Mill.) s mokrom sri. 11 Slika 2.3.1. Shema vezanja i umetanja molekula vode meu celulozni skelet (A) vezanje molekula vode vodikovim vezama u monomolekularnom sloju, (B) postupni nastanak monomolekularnog sloja, (C) polimolekularni sloj (prema Tsoumisu, 1991, str. 131). 24 Slika 2.4.1. Smanjenje mase drva smreke (Picea abies) nakon obrade razliitim temperaturama u trajanju 24 sata (Fengel i Wegener, 1984, str. 319) 28 Slika 2.4.2. Udjel sastojaka drva bora (Pinus sylvestris) nakon obrade razliitim temperaturama u trajanju 48 sati (Kollmann i Fengel, 1965) 29 Slika 2.4.3. Udjel sadraja polioza u drvu smreke (Picea abies) nakon razliitih temperatura obrade u trajanju 24 sata (Kollmann i sur., 1969) 30 Slika 2.4.4. Pregled skupina ekstraktiva s podskupinama i pojedinanim sastojcima ekstrahiranim parom i vodom (FENGEL i WEGENER, 1984) 33 Slika 2.4.5. Udjeli ekstraktiva nakon vrue i hladne ekstrakcije pri razliitim temperaturama obraene smrekovine (Picea abies) u trajanju 24 sata (Kollmann et al. 1969) 34 Slika 2.5.1. Histoloka graa poprenog presjeka drva jele (Abies alba Mill.) uz zonu kambija 42 Slika 3.1.1. Popreni presjek trupia sa ucrtanim poprenim presjecima etvrtaa 45 Slika 3.1.2. Slika etvrtae sa ispiljenim i oznaenim uzorcima 45 Slika 3.2.1. Dijagram toka sorpcijskog pokusa 46 Slika 3.2.2. Odnos izmeu bubrenja i vlanosti drva (Noack, Schwab i Bartz, 1973) 48 Slika 3.2.3. Zatvorena posuda za uravnoteenje vlage uzoraka drva iznad zasienih otopina soli, s ureajem za strujanje zraka, vlagomjerom i uzorcima. 49 TOC \o "7-7"Slika 4.1.1. Vlaga ravnotee neparene i parene bjeljike i sri jelovine pri temperaturi 20 C i 65%-tnoj relativnoj vlazi zraka. 52 Slika 4.1.2. Vlaga ravnotee neparene i parene bjeljike i sri jelovine pri temperaturi 20 C i 86%-tnoj relativnoj vlazi zraka. 53 Slika 4.1.3. Vlaga ravnotee neparene i parene bjeljike i sri jelovine pri temperaturi 20 C i 34%-tnoj relativnoj vlazi zraka. 54  TUMA OZNAKA SYMBOL 106 \f "GreekMathSymbols" relativna vlaga zraka ur vlaga ravnotee us poetna vlaga sirovog drva u65 vlaga ravnotee kod SYMBOL 106 \f "GreekMathSymbols"=65% u86 vlaga ravnotee kod SYMBOL 106 \f "GreekMathSymbols"=86% u34 vlaga ravnotee kod SYMBOL 106 \f "GreekMathSymbols"=34% SYMBOL 114 \f "GreekMathSymbols"0 gustoa drva u apsolutno suhom stanju R nominalna gustoa drva qT, qR diferencijalno bubrenje u tangentnom odnosno radijalnom smjeru hT, hR koeficijent bubrenja u tangentnom odnosno radijalnom smjeru qT/qR anizotropija bubrenja SYMBOL 98 \f "GreekMathSymbols"NT, SYMBOL 98 \f "GreekMathSymbols"NR inicijalno utezanje u tangentnom odnosno radijalnom smjeru SYMBOL 97 \f "GreekMathSymbols"T, SYMBOL 97 \f "GreekMathSymbols"R maksimalno bubrenje u tangentnom odnosno radijalnom smjeru 1. UVOD I POSTAVKA PROBLEMA Osravanje je fizioloki proces starenja drva koji je genetski uvjetovan. Prema tome, sasvim je jasno da svaka vrsta drva mora prije ili kasnije osriti. S tog stajalita mogue je izravno dokazivanje sri, tj. dokazivanje vitalnosti parenhimskog tkiva fiziolokim metodama koje mogu biti biofizikalne i/ili biokemijske (npr. FREY-WYSLING i BOSSHARD, 1959; HUGENTOBLER, 1965; NEESANSYMBOL 221 \f "Courier New CE", 1966. i 1968). Istodobno sa starosnim odumiranjem parenhimskog tkiva u njemu se stvaraju vee ili manje koliine niskomolekularnih ekstraktivnih tvari koje prodiru u stijenke stanica (npr. NEESANSYMBOL 221 \f "Courier New CE", 1968; HILLIS, 1968, 1971), pa glavne razlike u kemijskom sastavu bjeljike i sri treba traiti upravo u sadraju tih tvari. Niskomolekularne ekstraktivne tvari zauzimaju one prostore u staninoj stijenki u koje bi mogla ui voda kada ekstraktivnih tvari ondje ne bi bilo. Zato su posljedice prisutnosti niskomolekularnih tvari u staninim stijenkama sri, izmeu ostaloga, nie vrijednosti sorpcijskih svojstava (vlage ravnotee, bubrenja i utezanja) sri od bjeljike (npr. GHOONG i ACHMADI, 1991; SALAMON i KOZAK, 1968; TAYLOR, 1974; WANGAARD i GRANADOS, 1967). U strunoj se literaturi mogu nai opisi jele kao vrste koja stvara zrelo drvo ili suho drvo (engl. ripewood, njem. Reifholz) (WAGENFUHR, SCHEIBER, 1974; GROSSER 1977), ili drvo sa nediferenciranom sri (tal. con durame indifferenziato) (npr. GIORDANO, 1971), ili drvo bez obojene sri (njem. ohne Farbkern) (npr. SCHWEINGRUBER, 1978, 1990), pa takvi nazivi upuuju na nesporazume glede stanja sri kod jele. Meutim, BAUCH i sur. (1975) na temelju istraivanja fiziolokih parametara zakljuili su da jela (Abies alba Mill.) stvara sr. Osnovni je cilj ovog rada posrednom fizikalnom metodom dokazati postojanje sri u jele, tj. potvrditi postojanje niskomolekularnih tvari u staninim stijenkama sri njihovom posljedicom - stalno niom vlagom ravnotee, te manjim bubrenjem i utezanjem sri nego bjeljike. U praksi je poeljno poveati dimenzijsku stabilnost drva. Ona se moe poveati izlaganjem drva kemikalijama (KOLLMANN i COTE, 1968) ili povienim temperaturama tijekom razliitog vremenskog trajanja (HILLIS 1984). esto se zaboravlja da se svakim tehnikim suenjem drva na temperaturi vioj od 70 SYMBOL 176 \f "Courier New CE"C istodobno postie i dimenzijska stabilizacija drva (KOLLMANN, 1969). KININMONTH je 1976. ustanovio da su uinci temperature na stabilizaciju drva jai pri obradi vlanoga nego suhog drva. Drugi je cilj ovog rada dokazati da se parenjem postie poboljanje sorpcijskih svojstava bjeljike i sri jelovine.  Slika 2.1.1. Popreni presjek svjee posjeenog stabla jele (Abies alba Mill.) 2. OPI DIO 2.1. SR I OSRAVANJE Prema meunarodnom udruenju anatoma drva (Committee on nomenclature, IAWA, 1964; POLJARI, 1969), bjeljika je definirana kao "dio drva koji u ivom stablu sadri ive stanice i rezervne tvari (npr. krob)". Prema istom izvoru, sr ine "unutarnji slojevi drva koji u ivom stablu ne sadre ive stanice, a rezervne supstancije (npr. krob) uklonjene su ili transformirane u srne tvari. Sr je u pravilu tamnija od bjeljike, iako nije uvijek jasno diferencirana". Navedena odrednica ne objanjava svjetliju boju sri od bjeljike, to se vidi na svjee oborenom stablu jele (Abies alba Mill.) (slika 2.1.1), pa odatle i u uvodu spomenuti nesporazumi pri opisivanju jele. Tablica 2.1.1. Nazivi bjeljike i sri u razliitim jezicima (poljari, 1969) HrvatskiSlovenskiEngleskiFrancuskiNjemakiTalijanskiPortugalskipanjolskibjeljikabeljavasapwoodaubierSplintholzalburnoalburnoalburasrjedrovinaheartwoodbois parfaitKernholzcuorecerne ou durameduramen S etimolokog stajalita, pojam bjeljike uglavnom se odnosi na boju drva, a gdjekada se odnosi na vlanost, odnosno sonost. Pojam sri najee oznaava sredinji dio stabla, no gdjekad razumijeva i bolju kakvou u usporedbi s bjeljikom (tablica 2.1.1). Gledajui povijesno, strunjaci s podruja umarstva i prerade drva ve su davno primijetili vizualne razlike izmeu unutranjih i vanjskih slojeva drva, pa su na temelju toga predloili prva razvrstavanja drvea s obzirom na tip sri. Glavni nedostatak tih razvrstavanja bilo je nejedinstveno mjerilo. Jedanput je to bilo obojenje sri koje se redovito ili neredovito pojavljivalo, drugi put je to bila vlanost koja se vie ili manje razlikovala u sri i bjeljici, a trei put je to bila mjeavina tih dvaju svojstava. NSYMBOL 214 \f "Courier New CE"RDLINGER (1860, iz: MAYER-WEGELINA, 1955) dijelio je drvee na ono s izrazitom bojom sri (njem. KernbSYMBOL 228 \f "Courier New CE"ume, engl. heartwood trees), na ono kojemu su unutranji slojevi drva sui, dakle zreliji od bjeljike (njem. ReifholzbSYMBOL 228 \f "Courier New CE"ume, engl. ripewood trees), te na ono kojemu su unutranji slojevi drva po svim svojstvima jednaki vanjskima (njem. SplintbSYMBOL 228 \f "Courier New CE"ume, engl. sapwood trees). TRENDELENBURG (1939) i MAYER-WEGELIN (1955) daju prednost podjeli na osnovi boje, a zatim i na osnovi vlanosti, pa predlau skupine s obojenom sri (njem. mit gefSYMBOL 228 \f "Courier New CE"rbtem Kernholz) i one s neobojenom sri (njem. mit ungefSYMBOL 228 \f "Courier New CE"rbtem Kernholz), a zatim podskupine s izrazitom (njem. ausgeprSYMBOL 228 \f "Courier New CE"gtem) razlikom u vlanosti sri i bjeljike, bez izrazite razlike u njihovoj vlanosti, te sa umjerenom (njem. mSYMBOL 228 \f "Courier New CE"SYMBOL 223 \f "Courier New CE"igem) razlikom meu njima. Na temelju tadanjih spoznaja BOSSHARD (1965) je zakljuio da je osravanje najvanija primarna starosna pojava u ivom stablu i oznaava kvalitativnu promjenu u stablu, te da se bjeljika svake vrste drva mora prije ili kasnije preobraziti u sr. Kvantitativno se starenje zbiva u kambijevoj zoni kao sazrijevanje kambijskih derivata. Elementi mehanikoga i provodnog sustava ve nekoliko tjedana nakon diferencijacije izgube protoplast, pa su promjene toga tkiva u osravanju sasvim pasivne. Istodobno se sintetiziraju i u stanine lumene i stijenke odlau srne tvari. Provodno i mehaniko stanije time je morfoloki i fizioloki fiksirano (tablica 2.1.2). Na temelju fiziolokih promjena tijekom osravanja BOSSHARD je 1966. nainio novo imenovanje razliitih tipova sri nastojei pomiriti dotadanje nesporazume glede vidljivosti promjena boje zbog osravanja (tablica 2.1.3). U to je vrijeme ta terminologija odgovarala znanstvenim dostignuima na tom podruju, ali je s novim spoznajama postala zbunjujua. Prema SHIGO-vu (1986) miljenju, zabuna je nastala uvrtavanjem ozljedama uzrokovanih promjena drva meu srne pojave (vidi dalje). Tablica 2.1.2. Proces starenja u kambiju i ksilemu (Bosshard 1974) tkivo jedinica vremena dt (jedno vegetacijsko razdoblje ili krae)vrijeme t (vie vegetacijskih razdoblja)KAM- BIJ I - sloj vretenastih inicijalaKVAN- TITA- TIVNO - usporavanje diobenog procesa  - rast inicijala u duinu do maksimalne vrijednosti - poveanje broja inicijala ZONA - sloj inicijala trakova STA-  - usporavanje diobenog procesa  - poveanje broja incijala - irenje trakovnog sustavaKAM- BIJA  - tkivo materinskih stanicaRENJE  - diferencijacija stanica - stvaranje sekundarnog sloja stijenkeKSI-  - mehaniko tkivoKVALI-  - gubitak protoplazme - potpuna lignifikacija LEM - provodno tkivoTATIV- NO  - gubitak protoplazme - potpuna lignifikacija - aspiracija jaica u traheidama - blokada traheja tilama - priuvno (parenhimsko) tkivoSTA- RENJE - gubitak sposobnosti dijeljenja stanica - tvorba srnih tvari - tvorba tila - postupna nekrobioza Prema HILLISU (1987), postoje dva tipa sri. Prvi je tip otro ogranien po granici goda i naziva se prava (engl. regular) (npr. u rodova Quercus, Robinia, Pinus). Drugi se tip sri jeziasto iri u bjeljiku i naziva se neprava (engl. irregular) (npr. u vrsta i rodova Fagus sylvatica, Acer, Betula, Carpinus, Fraxinus). Oito je da u nepravu sr HILLIS svrstava diskolorirano drvo, a prema toj podjeli nije jasno kamo pripada jela. Tablica 2.1.3. Nazivi razliitih tipova osravanja u razliitim jezicima (Bosshard, 1966) Vrsta drvaNjemakiEngleskiSlovenskiHrvatskiAbies albaBaum mit hellem Kernholzwood having light heartwooddrevo s svetlo jedrovinodrvo sa svijetlom sriCarpinus betulusBaum mit verzSYMBOL 246 \f "Courier New CE"gerter Kernholzbildungtree with retarded formation of heartwooddrevo z upoasnjeno ojedritvijodrvo s odgoenim osravanjemQuercus roburBaum mit obligatorischer Farbkernholzbildungwood with obligatory colored heartwooddrevo z obligatno obarvano jedrovinodrvo s obvezatno obojenom sriFagus sylvatica, Fraxinus excelsiorBSYMBOL 228 \f "Courier New CE"ume mit fakultativer Farbkernholzbildungwoods with facultatively colored heartwooddrevesa z fakultativno obarvano jedrovinodrvee s fakultativno obojenom sri 2.1.1. Prijelazna zona Prijelaznim se drvom (engl. intermediate wood) smatraju "unutarnji slojevi (godovi) bjeljike, po boji i svojstvima na prijelazu izmeu bjeljike i sri" (IAWA, 1964; POLJARI 1969). HILLIS (1987) definira prijelaznu zonu (engl. transition zone) kao "usku, blijedo obojenu zonu koja okruuje neke sri i oteene dijelove, esto sadri ive stanice, obino bez kroba, nepermeabilna za tekuine, nieg sadraja vode od bjeljike, a ponekad i sri." Isti autor navodi da se oba pojma u starijoj literaturi podjednako rabe te i sam nije uspio razjasniti prema kakvom naelu, vjerujui da oba naziva oznaavaju istu zonu. Mogue je takoer i objanjenje da intermediate wood odgovara neprovodnoj bjeljici, a transition zone (njem. Ubergangszone) mjestu preobrazbe bjeljike u sr. Prema HILLISU (1987), prijelazno se drvo (intermediate wood) katkad moe zamijeniti i u obine jele (Abies alba Mill.), na poprenom presjeku trupia ima varirajuu irinu, od 5 do 10 mm, i sadraj vode nii nego u bjeljici, slian sadraju vode sri. Kako je koliina ekstraktiva niska, prijelazno je drvo esto bljee od susjednih zona. Vjerojatno je da zbog navedenih obiljeja pojam prijelaznog drva (intermediate wood) u starijoj literaturi (NSYMBOL 214 \f "Courier New CE"RDLINGER, 1860; iz: HILLIS, 1987) koriten u jednakom smislu kao isuina, tj. zrelina (engl. ripewood, njem. Reifholz), to je takoer mogue protumaiti kao neobojenu sr. 2.1.2. Vlanost Sadraj vode u ivom stablu kree se u irokom rasponu od 30 do 300% (GIORDANO, 1971), a ovisi o vrsti drva, poloaju u stablu i godinjem dobu. Voda u stablu slui kao prijenosni medij za anorganske ione (transpiracijski tok) i asimilate (asimilacijski tok), kao sirovina za fotosintezu i sredstvo za hlaenje. Okomita i vodoravna raspodjela vlage u deblu odraz je funkcije sekundarnoga ksilema. U etinjaa i difuzno poroznih listaa povrina provodnog presjeka u korelaciji je s veliinom transpiracijske povrine i korijenova sustava. S rastom u debljinu provodna se bjeljika pomie na periferiju, a srednjica se isuuje (nastanak zreline odnosno suine). U prstenastoporoznih listaa samo periferni dio bjeljike provodi vodu, a unutarnji slui za pohranu priuvnih tvari (ZIEGLER 1968). U etinjaa se vlanost prema sredini poprenog presjeka stabla smanjuje, a u sri se pribliava toki zasienja staninih stijenki (npr. u jele, slika 2.1.2). U vrsta bez sri vlanost se ravnomjerno smanjuje prema sriki, ali nikada nie od toke zasienosti staninih stijenki (npr. u bukve). ini se da isuivanje prethodi osravanju. Postoje pokazatelji da se to dogaa kada se omjer vode i plina u staninim upljinama snizi. Slian proces potie i ozljeda. Prema HILLISU (1987), postoji neposredna veza izmeu isuivanja i vitalnosti ivih stanica. ini se da isuivanje bjeljike na prijelazu u sr pridonosi preusmjeravanju metabolizma ivih stanica trakova od glikolize prema proizvodnji ekstraktivnih tvari. Oboljela stabla jele (Abies alba Mill.) imaju manju vlanost bjeljike, a veu vlanost sri nego zdrava (npr. SHORTLE i BAUCH, 1986). EMBED Excel.Chart.5 \s \* mergeformat Slika 2.1.2. Raspored sadraja vode po poprenom presjeku jele nakon ruenja (Sinkovi, 1994) U nekih rodova drvea sr katkada moe sadravati i vie vode nego bjeljika (npr. Ulmus, Populus, Carya, Quercus, Nyssa, Juglans, Abies) (HILLIS 1968). Takvu sr nazivamo mokrom sri. Pojava mokre sri u jele (Abies alba Mill.) moe biti jedan od znakova slabljenja vitalnosti stabala (npr. BAUCH i sur. 1975; TORELLI i sur. 1986.). Prema SHIGU i HILLISU (1973), pojava mokre sri u jele moe se protumaiti kao prvi stupanj reakcije stabla na ozljedu. Oni smatraju da nakon ranjavanja izloena bjeljika diskolorira, to je prvi dio reakcije stabla na mehaniko oteenje (prvi stupanj). Diskolorirano drvo prvog stupnja stvara se u stablima kao to su vrste javora, koji normalno ne stvaraju obojenu sr, kao i u bjeljici vrsta koje stvaraju sr poput hrasta. Diskolorirano drvo prvog stupnja u mnogim je svojstvima slino sri i donekle je otporno na mikrobioloku razgradnju. Sr i diskolorirano drvo prvog stupnja nazvani su zatitno drvo (engl. protective wood) zbog poveane otpornosti na razgradnju. Sr i diskolorirano drvo prvog stupnja razgrauju se djelovanjem mikroorganizama i njihovih pratilaca prelazei u drugi stupanj procesa razgradnje. Diskolorirano drvo u drugom stupnju postaje manje otporno na daljnju razgradnju koja dosee vrhunac u treem stupnju i fizikom propadanju drva. esto se zaboravlja da je mokra sr jele, osim to je mokra, ujedno i diskolorirana (slika 2.1.3), a crveno srce bukve, osim to je dikolorirano, ima i veu vlanost od perifernih ivih tkiva, to upuuje na to da pripadaju zatitnom drvu, odnosno prvoj fazi diskoloriranog drva nastalog nakon ozljede stabla.  Slika 2.1.3. Popreni presjek svjee posjeenog stabla jele (Abies alba Mill.) s mokrom sri. 2.1.3. Blokiranje provodnih putova Funkcioniranje provodnih putova za stablo je od ivotnog znaenja. U odreeno vrijeme stablo iskljui dio provodnog sustava koji mu nije vie potreban za opskrbu kronje. Na taj se nain drvo titi od embolije, a oteana je i zaraza. U procesu osravanja promijenjeno tkivo u samoj sri ima blokirane provodne putove (npr. PETRI 1971; ZIMMERMANN 1983). Dva su osnovna naina blokade provodnih putova u sri: aspiracija ograenih jaica u etinjaa i otiljavanje u listaa (PETRI, 1971). Aspiracija jaica je pojava da torus ograenih jaica etinjaa nalegne na porus. Samo vrste drva iz porodice Pinaceae, kojoj pripada i jela, imaju potpuno razvijen torus (LIESE, 1965). U prolosti se aspiracija smatrala posljedicom razliitih tlakova izmeu susjednih traheida, koji se javljaju radi isuivanja drva. HART i THOMAS (1967) aspiraciju jaica objanjavaju postupnim poveanjem kapilarnih sila zbog povlaenja vode u sve sitnije kapilare. BROOKER (1989) istu pojavu objanjava dinamiki. Traheide se vrlo brzo sue. Kada meniskus zrak - voda doe do jaice, tekuina se na drugoj strani kree vrlo brzo. Kako se stupac vode brzo zaustavlja, on djeluje na torus velikom dinamikom kratkotrajnom silom, koja ga deformira. Hoe li se jaica zatvoriti, ne ovisi o povrinskoj napetosti tekuine, nego ili o kohezijskoj vrstoi tekuine, ili o maksimalnoj adhezijskoj sili izmeu tekuine i stanine stijenke. Aspiraciju jaica meu prvima je primijetio PHILLIPS (1933). Neaspirirane jaice bjeljike aspiriraju se u prijelaznoj zoni, koja ima vlanost kao bjeljika i ive stanice parenhima. Tile su anatomska pojava u listaa koja je openito povezana s nastankom sri, no vrlo je esta i u bjeljici. Moe biti genetski odreena znaajka pojedinih vrsta, koja nije povezana s osravanjem (Quercus, Fraxinus, Robinia), a moe biti i odgovor na ozljedu. Tile su uvijek prisutne u bjeljici onih vrsta koje ih imaju i u sri. Nastaju ispupenjem sadraja parenhimskih stanica u susjedne traheje. Pojava je posljedica embolije (ZIMMERMANN, 1983), a uvjet je da su otvori membrana jaica na lancima traheja vei od 10 mm. Ako su otvori membrana jaica manji, traheje se zaepljuju polifenolima i gumastim tvarima. 2.1.4. Sazrijevanje radijalnog parenhima U bjeljici normalnog drva brojnih etinjaa (npr. borova) nalazimo parenhimske stanice radijalnog i aksijalnog sustava koje nemaju sekundarnih zadebljanja ni lignifikacije stijenki. U procesu starenja bjeljike ili pri preobrazbi bjeljike u sr stijenke stanica poinju odebljavati i lignificirati ve u zoni kambija (npr. Haploxylon skupina) ili lignificiraju tek na granici bjeljike i sri (npr. Diploxylon skupina) (BAUCH i sur., 1974). U sri nekih vrsta etinjaa opaena su lignificirana leasta zadebljanja ograenih jaica, a u bjeljici su leasta zadebljanja sastavljena uglavnom od pektina i odreene koliine celuloze i hemiceluloza (BAUCH i sur., 1968). I aksijalni smolni kanali u roda Pinus osravanjem lignificiraju. Lignifikacija i smrt parenhimskih stanica vremenski se podudaraju. Novonastale zrele stanice preuzimaju skladinu ulogu starijih stanica u sredini stabla. U tom se smislu veina autora slae s teorijom prema kojoj je osravanje mehanizam koji kontrole koliine bjeljike (npr. BAMBER, 1967a, b). 2.1.5. Biokemijske promjene Srne tvari proizvode parenhimske stanice u najstarijim slojevima bjeljike, tj. u prijelaznoj zoni. HIGUCHI (1969) pretpostavlja da se srne tvari i njihovi prethodnici veinom sintetiziraju u bjeljici, i to u njezinim najstarijim dijelovima, tj. u prijelaznoj zoni, jer je pri spajanju radioaktivnih sastojaka u razliite frakcije drvnih ekstraktiva primijetio da je metabolina aktivnost u tom dijelu drva dovoljno visoka za sintezu srnih tvari, iako je nia nego u kambijevoj zoni. Pri respiraciji u kambijevoj zoni prevladavaju glikoliza i TCA ciklus. U unutarnjoj bjeljici raste udjel pentoza-fosfatnog puta, koji pridonosi nastajanju cimetne kiseline kao predznaka srnih ekstraktiva. Biokemijske promjene u parenhimskim stanicama imaju sljedei tok: 1. Lignifikacija stijenki parenhimskih stanica trakova zapone u procesu starenja sintezom fenilalanin-amonij-lijaze. Pri lignifikaciji neiskoritene fenolne tvari uzrokuju disorganizaciju mitohondrija, u kojima se, izmeu ostaloga, nalaze enzimi i dodatni imbenici za tvorbu aktivirane octene kiseline, Krebsova ciklusa, dinog lanca, ukljuujui sustave oksidativne fosforilacije. Reakcije tako ne teku putem normalne oksidativne razgradnje i nagomilavaju se meuproizvodi odnosno ishodini proizvodi potrebni za sintezu srnih tvari (npr. terpenoida i A-prstena flavonoida). 2. Istodobno se prerada eera u parenhimskim stanicama preusmjeri od glikolize i Krebsova ciklusa prema pentoza-fosfatnom putu i prema sintezi B-prstena flavonoida i stilbena. Tako i ZIEGLER (1968) misli da nagomilani fenolni inhibitori uzrokuju disorganizaciju mitohondrija i omoguuju biosintezu srnih ekstraktiva. Fenolne tvari koje nastaju u parenhimu trakova vie su ili manje otrovne, pa se moraju ili premjestiti ili odloiti u vakuole koje okruuje tonoplast. Kad koncentracija fenolnih tvari naraste do odreene vrijednosti, tonoplast popusti. Fenolne tvari to ih je tonoplast dotada zadravao dou u dodir s hidrolazom, fenoloksidazom i peroksidazom u citoplazmi i staninoj stijenki. To omogui hidrolizu fenolnih glikozida u oksidativnu polimerizaciju. Opisana se prerada zbiva u stanicama trakova najstarijih dijelova bjeljike (prijelazna zona), npr. pod utjecajem etilena. Poveanje sadraja bjelanevina u unutranjoj bjeljici i prijelaznoj zoni ZIEGLER (1968) pripisuje enzimima koji sudjeluju pri tvorbi srnih tvari. One se sintetiziraju u parenhimskim stanicama trakova bjeljike i prijelazne zone iz uskladitenih ili iz listova premjetenih eera i masti. Biokemijske promjene u bjeljici ujedno uzrokuju i biofizikalne promjene (NEESANY 1966,1968). Prouavajui stvaranje mokre sri jele (Abies alba Mill.) BAUCH i sur. (1975) ustanovili su da se udjel eera i respiracijska aktivnost ivih stanica smanjuju od kambija prema srici, pa su zakljuili da se u jele stvara sr neovisno o sekundarnim promjenama koje se javljaju u mokroj sri. Koncentracija polifenolnih tvari u kapilarnoj tekuini mokre sri bila je nekoliko puta vea nego u bjeljici. 2.1.6. Ultrastrukturne i citoloke promjene U vanjskom dijelu bjeljike u ivim parenhimskim stanicama smjetene su citoplazmatske organele kao to su mitohondriji, Golgijevi aparati, endoplazmatski retikulumi, plastidi, ribosomi i lipidne kapljice vane za njihov ivot. Mitohondriji su osobito izraziti u doba rasta jer su tada respiracijska i proteinska sinteza vrlo aktivni fizioloki procesi. S fiziolokog stajalita osravanje je vremenski i prostorno omeeno na podruje prijelazne zone. Cjelokupni je proces mogue razumjeti u smislu uvodnog stupnja, tj. prestanka obavljanja provodne funkcije, i zakljunog stupnja koji odgovara neposrednoj preobrazbi bjeljike u sr. U unutarnjoj su bjeljici citoplazmatske organele manje brojne i aminoplasti su manje izraziti. U prijelaznoj zoni parenhimske stanice pokazuju tipinu vakuolizaciju, organele su potisnute na rub citoplazme. FREY-WYSSLING i BOSSHARD (1959) ustanovili su da prvotno eliptine jezgre parenhimskih stanica trakova s poveanjem udaljenosti od kambija postaju sve okruglije, manje i potpuno nestanu u sri, katkad mnogo prije granice sa sri. S udaljenou od kambija smanjuje se i reduktivna sposobnost mitohondrija za boju Janus green B. Za sintezu srnih tvari nuna je veza svih parenhimskih stanica jednoga traka s kambijevom zonom. Autori misle da se aerobioza na odreenoj udaljenosti od kambija promijeni u anaerobiozu. Neki metaboliti respiracijskog supstrata slue kao primatelji vodika, pa zato nastane vie ugljikova dioksida nego to se upotrijebi kisika. Promijenjeni uvjeti potiu stvaranje neobojenih fenola. Vjerojatno vei dio fenola nastane i u unutarnjoj bjeljici i vanjskom dijelu prijelazne zone. Ipak, promjena oblika jezgre nije nuno povezana s aktivnou stanica, jer u trepetljike i breze (vrste bez sri) jezgre nestanu ve u 12. ili 13. godu od kambija. Nije potpuno jasno to za stanicu znai gubitak jezgre. Prouavanja razliitih enzimskih sustava pokazala su da je aktivacija enzima nespecifian fenomen. Kako se ini da je povezan s poveanom koliinom polifenola, njihova je uloga vjerojatnije povezana s polimerizacijom (smeenjem) polifenolnih monomera nakon njihova nastanka (HILLIS, 1987). Nije nuno da se svi enzimski sustavi, prije svega oni u staninoj stijenki, deaktiviraju kad jezgra propadne i kad prestanu normalne fizioloke funkcije. U prijelaznoj zoni zabiljeen je i porast nekih u vodi topljivih vitamina koji ine koenzime pri sintezi A-prstena flavonoida, kojima pripada i veina srnih tvari. U nekih vrsta (oraha, bagrema, trenje) neposredno prije nastank sri opaene su jezgre poveanog indeksa vitkosti (HUGENTOBLER, 1965). Istodobno se poveao i broj nukleola u jezgri, to bi moglo znaiti poveanu produkciju RNK, a time i pojaanu sintezu bjelanevina. To govori o pojaanoj aktivnosti u prijelaznoj zoni u vrsta s obligatno obojenom sri, tj. gdje postoje izrazite razlike izmeu bjeljike i sri. FENGEL (1970) opazio je da se tamni globularni dijelovi povezani s vakuolama u parenhimskim stanicama trakova u cijeloj bjeljici sele preko plazmodesmata u tangentnim stijenkama. U unutranjoj bjeljici, na samoj granici sa sri, tamni se materijal iz vakuola razgradio i premjestio kroz srednju lamelu u jainu membranu i staninu upljinu. 2.1.7. Evolucijski pogledi na osravanje Osravanje nije nita manje opsean i vaan proces u prirodi od lignifikacije. Istraivanja biogeneze lignina i srnih tvari su pokazala da oba procesa teku usporedno. Lignin i tvari koje se odlau u procesu osravnja sekundarne su biljne tvari. Pojam sekundarno ne znai da su te tvari nevane, nego oznaava sekundarnost u smislu biosinteze. One nisu bitne za ivot, za razliku od primarnih metabolita, koji su zajedniki svim stanicama i slue bitnim ivotnim procesima kao to je biosinteza nukleinskih kiselina, lipida, ugljikohidrata i bjelanevina. Glavne srne tvari i lignin fenilpropanoidne su tvari. Njihova je pojava tijekom evolucije omoguila nastanak velikih i visokih drvenastih biljaka. Lignin je pridonio veoj vrstoi traheja, vlakana i, openito, staninih stijenki, a srne tvari svojim fungicidnim i insekticidnim djelovanjem poveavaju trajnost drvnog tkiva. Sve je to utjecalo na pojaanje rasta biljaka u visinu. ini se da je evolucija lignifikacije i osravanja u tijesno povezana s izluivanjem u biljaka. S nastankom veih oblika omjer povrine i volumena sve je manji, a time su i mogunosti djelotvornog izluivanja manje. U viih se biljaka izluivanje obavlja manjim dijelom preko korijenja i lia, a biljke uglavnom zadre veinu sekundarnih tvari u sebi, s tim da su pojedine stanice ovisne o izluivanju u vakuole i stanine stijenke. Srne tvari nastaju iz istih derivata cimetove kiseline koji su i meutvari pri tvorbi lignina. Problem izluivanja otpadnih preraevina priroda je rijeila njihovom preradom u lignine, flavonoide i ostale sekundarne tvari. Na izluivanju se temelji STEWARTOVA (1966) teorija osravanja i nastanka tila. Odumiranje parenhimskih stanica Stewart pripisuje translokacijskom izluivanju. Izluevine koje se ne skupljaju u vakuolama stanica trakova premjetaju se u smjeru srike gdje se nagomilaju i pri odreenoj, letalnoj, koncentraciji prouzroe smrt parenhimskih stanica sa svim znanim posljedicama. Osravanje se moe promatrati i u funkciji homeostaze (ravnotee) (TORELLI, 1997). Koliina bjeljike u ivom je stablu u ravnotei s koliinom kronje i korijenja. Lisna, tj. fotosintetizirajua i transpirirajua povrina ne poveava se nakon odreene starosti stabla, dok promjer debla i dalje raste. Da bi se zadrala spomenuta ravnotea, stablu je potreban mehanizam za uklanjanje ostarjelih dijelova. Kako stablo ne moe te dijelove fiziki odbaciti ili preraditi, oni bre ili sporije umiru. Kada se to ne bi dogaalo, stablo bi, da prehrani sve veu koliinu stanica, stalno moralo poveavati kronju. Ako se kronja ne bi poveavala, suzili bi se godovi, ili bi stablo prestalo raati, a to bi znailo prestanak razmnoavanja. Uklanjanje ostarjelih dijelova u stablu, koje je u funkciji homeostaze, zbiva se na dva naina. Prvi je osravanje (npr. u hrasta), a drugi isuivanje (npr. u bukve) sredinjeg dijela debla. Osravanjem stabla zbivaju se opisane biokemijske promjene u stanicama parenhima najstarijih godova bjeljike, a isuivanjem se polako i postupno smanjuje vitalnost i potreba stanica za energijom idui od kambija prema sriki. Oba naina uklanjanja ostarjelih tkiva imaju zadau odranja ravnotee radi omoguivanja daljnjeg rasta i razmnoavanja drvea. 2.2. RAZLIKE IZMEU BJELJIKE I SRI; OSVRT NA JELU 2.2.1. Kemijske razlike u bjeljici i sri moe biti razliit udjel glavnih kemijskih sastojaka drva, no TIMELL (1986) upozorava da se ne smije zaboraviti kako esto bjeljika pripada zrelom (adultnom) drvu, a sr nezrelome (juvenilnom) drvu, pa iz toga proizlaze i razlike u sadraju lignina i polisaharida. Vjerojatno se polisaharid vrlo malo mijenja kada se jednom odloi u sekundarni sloj stijenke. FREEMAN R.D. (1946) smatra da u drvu etinjaa openito ima vie ekstraktiva u sri nego u bjeljici, a celuloze i lignina manje u sri nego u bjeljici. Nadalje, sadraj acetilnih skupina vei je u bjeljici nego u sri svih etinjaa i veine listaa. Prema samoj definiciji, bjeljika obiluje hranjivim tvarima kao to su krob, eeri i lipidi. One se nalaze u parenhimskim stanicama, a bjeljika jele uglavnom sadri krob i lipide (KRAMER i KOZLOWSKI, 1979, prema HILLISU, 1987, str. 13). Kapljice lipida mijenjaju se i poveavaju u bjeljici na granici sa sri u jele (Abies alba Mill.) (FREY-WYSSLING i BOSSHARD, 1959), a krob nestaje na granici bjeljike i sri. Osim poveanja hidrolize kroba s udaljenou od kambija, u bjeljici drva jele primijeeno je istodobno poveanje broja fenolnih vakuola u kojima se stvaraju polifenoli (PARAMESWARAN i BAUCH, 1975). Torusi membrana ograenih jaica bjeljike jele (Abies alba Mill.) ne sadre lignin (BAUCH i sur., 1968). Uglavnom su sastavljeni od pektina te ograniene koliine celuloze i hemiceluloza. Tijekom osravanja u torusima ograenih jaica traheida jele (Abies alba Mill.) stvara se lignin, a torusi se jo oblau dodatnim aromatskim sastojcima (BAUCH i sur. 1968; BAUCH i BERNDT, 1973). Osim u parenhimskim stanicama traka, fenolne se tvari u jelovunu nalaze i u jainim membranama traheida bjeljike, no u sri ih ima vie (PARAMESWARAN i BAUCH, 1975; BAUCH i BERNDT, 1973). Glavne kemijske razlike izmeu bjeljike i sri ipak treba traiti u sadraju ekstraktiva. Kao to je ve navedeno, on je najee vei u sri nego u bjeljici, a sastav ekstraktiva u normalnom drvu odreene vrste vie je ili manje stalan, to omoguuje kemotaksonomiju. Smolasti, polifenolni i ostali ekstraktivi gotovo su uvijek smjeteni u parenhimskim stanicama bjeljike, a koliina im se poveava stvaranjem sri (HILLIS, 1968). Ekstraktivne tvari sri mogu biti odloene u staninim stijenkama, mogu ih oblagati u tanjem ili debljem sloju te mogu oblagati membrane ograenih jaica (KRAHMER i COTE, 1963; KUO i ARGANBRIGHT, 1980a,b). HILLIS (1971) tvrdi da se veina ekstraktiva nalazi u staninim upljinama, iako su znaajne koliine prisutne i u staninim stijenkama sri. Hillis takoer misli da su slobodni prostori u staninoj stijenci dovoljno veliki da dopuste penetraciju velikog broja polifenola i drugih tvari. Pri ekstrakciji vodom ukloni se 16% ekstraktiva iz staninih stijenki drva Sequoia spp (TARKOW i KREUGER, 1961). Najvanije srne tvari su aromati, meu njima flavonoidi, Meu koje pripada veina srnih tvari, u manjem opsegu pojavljuju se masne kiseline i izoprenoidne tvari. KUO i ARGANBRIGHT (1980b) primijetili su da u drva Sequoia sempervirens i Libocedrus decurens polifenolni ekstraktivi oblau stijenke traheida, te da su obloenije stijenke onih traheida koje su blie parenhimskim stanicama traka. Takoer su uoili da se polifenolni ekstraktivi koji ulaze u staninu stijenku infiltriraju u smjeru suprotnome slijedu lignifikacije kako ga predlau WARDROP (1964) te KUTSCHA i SCHWARZMANN (1975). U usporedbi s obinim borom (Pinus sylvestris L.) (tablica 2.4.1), jelovo drvo ima malo ekstraktiva. Koliina fenolnih ekstraktivnih tvari jo je manja, a u sri ih je vie nego u bjeljici (tablica 2.4.1). 2.2.2. Razlike u fizikalnim svojstvima Boja sri je moda najvidljivije fizikalno svojstvo drva, pa stoga moe i obmanuti jer sama po sebi ne znai postojanje sri i srnih tvari (npr. Fagus sylvatica L., Abies alba Mill.). Tvari koje se neutralnim otapalima mogu ukloniti iz stanine upljine i stijenke vie ili manje odreuju mnoga svojstva koja razlikuju bjeljiku od sri. Na temelju pregleda literature HILLIS (1968) meu ostalim svojstvima navodi dimenzijsku stabilnost, gustou, permeabilnost i tvrdou kao neka od obiljeja drva na koja utjeu ekstraktivi. Za svojstva bubrenja i utezanja, kao i za dimenzijsku stabilnost, osim koliine, vrlo je bitan i poloaj ekstraktivnih tvari, tj. nalaze li se u stijenkama ili u upljinama stanica. Ekstraktivi su uglavnom smjeteni u parenhimskim stanicama, i to u stijenkama (obligatno obojena sr) i u lumenima (fakultativno obojena sr), to je ovisno o kemizmu njihove sinteze (NEESANSYMBOL 221 \f "Courier New CE", 1966,1968; BOSSHARD 1968). Kod fakultativno obojenih sri prevladavaju prije svega (slabije izraene) kavalitativne promjene koje se iskazuju oksidacijskim, kondenzacijskim i polimerizacijskim reakcijama, pri emu se prethodne srne tvari oboje i postanu tee topljive u usporedbi s tvarima u bjeljici (BOSSHARD, 1968). Ekstraktivi utjeu na odnose drvo - voda. Vrste drva sa relativno malom koliinom ekstraktiva mogu sadravati vee koliine vode u staninim stijenkama nego to to mogu vrste sa veim sadrajem ekstraktiva. Uklanjanje ekstraktiva poveava kapacitet stanine stijenke za vodu, a time poveava i utezanje i bubrenje drva (SALAMON i KOZAK, 1968). U vrsta drva u kojih ekstraktivne tvari ne prodiru u stijenke stanica utezanje se poveava s poveanjem gustoe drva (BOSSHARD, 1968). Na primjeru drva Beilschmiedia tawa Benth. et Hook, tipinog drva s fakultativno obojenom sri, BOSSHARD (1968) je pokazao da su mikrotehnoloka mjerenja utezanja i sorpcije pogodna za odreivanje poloaja srnih tvari, tj. utvrivanja nalaze li se one u stijenkama ili u upljinama stanica. Za dimenzionalnu stabilnost drva vana je koliina lignina, jer on zauzima prostore u staninim stijenkama koje bi mogla zauzeti voda. Nelignificirane stijenke uteu se vie od lignificiranih (WARDROP, 1975) i imaju veu sklonost upijanju vode nego lignificirane stijenke (POPPER i BOSSHARD, 1976). Gustoa sri u vrsta s obojenom sri malo je vea nego gustoa bjeljike upravo zbog veeg udjela ekstraktiva. Osravanje nema znatnijeg utjecaja na mehanika svojstva drva. Zbog zaepljenosti provodnih putova, drvo sri redovito slabije proputa tekuine i plinove nego drvo bjeljike. Drvo sri esto je trajnije, tj. prirodno otpornije na napadaj gljiva i kukaca nego drvo bjeljike. 2.3. HIGROSKOPNOST, SORPCIJA I RAVNOTENA VLAGA S OBZIROM NA OSRAVANJE Higroskopnost je svojstvo drva da upija vlagu iz okolne atmosfere i da je zadrava u obliku tekue vode ili vodene pare u ravnotei s vodenom parom okoline. To svojstvo proizlazi iz kemijskog sastava drva i zbog njega je drvo uvijek vie ili manje vlano. Higroskopnost je vano svojstvo jer vlaga koju drvo sadri utjee na sva ostala njegova svojstva. To je nepoeljno svojstvo drva kao materijala s gledita njegove dimenzijske stabilnosti. Koliina higroskopski vezane vode ograniena je brojem sorpcijskih mjesta koja lako veu molekule vode, a to su slobodne -OH skupine hemiceluloza, celuloze, lignina i nekih ekstraktiva. Pri adsorpciji voda se vee na hidroksilne skupine, celulozni se skelet iri, a stanina stijenka bubri (slika 2.3.1). Vlanost drva u stanju higroskopske ravnotee jest ravnotena vlaga drva (ur). Ona se razlikuje u ovisno o relativnoj vlazi zraka, temperaturi, vrsti drva, sadraju ekstraktiva, prethodnoj obradi drva i njegovim mehanikim naprezanjima. Desorpcijske i adsorpcijske krivulje koje dobivamo za drvo postupnim uravnoteenjem u padajuim i rastuim relativnim vlanostima zraka pri stalnoj temperaturi sigmoidne su, tj. pokazuju histerezu. Krivulja desorpcije lei iznad krivulje adsorpcije. Radi strukturnih i kemijskih razlika, histereze se za razliite vrste drva meusobno razlikuju.  Slika 2.3.1. Shema vezanja i umetanja molekula vode meu celulozni skelet (A) vezanje molekula vode vodikovim vezama u monomolekularnom sloju, (B) postupni nastanak monomolekularnog sloja, (C) polimolekularni sloj (prema Tsoumisu, 1991, str. 131). Razlika u ravnotenim vlanostima dobivenim u adsorpciji i desorpciji izraava se njihovim meusobnim omjerom A/D i po pravilu je najvea u podruju relativne zrane vlanosti od 60 do 80%. URQUHART i sur. (1924, i 1929; iz KOLLMANN i COTE, 1968, str. 192) objanjavaju histerezu time to se hidroksilne grupe celuloze i lignina u drvu za vrijeme suenja priblie i meusobno zasite. Pri adsorpciji neke hidroksilne skupine ostaju i dalje meusobno zasiene ne doputajui ulazak molekulama vode, pa je ravnotena vlanost za vrijeme adsorpcije nia. Histerezu je mogue objasniti i termodinamiki (CHRISTENSEN i KELSEY, 1959). Drvo nije potpuno elastino, pa utezanje i bubrenje uzrokuju deformacije, a one pak rezultiraju naprezanjima. S vlanou se smanjuju plastina preoblikovanja kojima su uvjetovani razliiti energijski gubici pri adsorpciji i desorpciji. Zato sorpcijske izoterme gela koji bubri pokazuju razlike u brzini promjene vlanosti u odnosu prema promjeni relativne zrane vlanosti meu adsorpcijom i desorpcijom. Brzina promjene ravnotene vlanosti vea je u procesu desorpcije od apsolutne suhoe do kvazilinearnoga podruja nego u procesu adsorpcije. Krivulja je u oba primjera konveksna. Pri viim relativnim zranim vlanostima (tj. onima iznad kvazilinearnog podruja) proces desorpcije se uspori, tako da je brzina adsorpcije vea, a obje su krivulje konkavne. Toka infleksije je u kvazilinearnom podruju. Do toke infleksije (duAds/dSYMBOL 106 \f "GreekMathSymbols") < (duDes/dSYMBOL 106 \f "GreekMathSymbols")(d2ur/dSYMBOL 106 \f "GreekMathSymbols"2) < 0sAds < sDes Iznad toke infleksije(duAds/dSYMBOL 106 \f "GreekMathSymbols") > (duDes/dSYMBOL 106 \f "GreekMathSymbols") (d2ur/dSYMBOL 106 \f "GreekMathSymbols"2) > 0sAds > sDes Na sorpcijska svojstva utjeu i srne tvari (ekstraktivi), veinom polifenoli (flavanoidi, lignani, tanini). Oni su preteno utisnuti u staninoj stijenci i zauzimaju prostor u koji bi mogla ui voda. Dio srnih tvari moe se pri viim temperaturama rastopiti u adsorbiranoj vodi, to poveava higroskopnost drva. Uinak ekstraktiva na sorpciju najvidljiviji je u gornjem podruju relativne vlanosti zraka (WANGAARD i sur. 1967; CHOONG i ACHMADI, 1991). Drvo s mnogo ekstraktiva u staninim stijenkama manje je higroskopno, pa se zato i slabije utee (CHOONG 1969; CHOONG i FOGG 1989) (tablica 2.3.1). BLAND (1971) misli da polifenoli to se nalaze u staninoj stijenci spreavaju stvaranje izravnih vodikovih veza izmeu oblinjih hidroksilnih skupina susjednih celuloznih mikrofibrila i tako nain omoguuju slabljenje unutranjih naprezanja (relaksaciju), a svojim nagomilavanjem vjerojatno i ograniuju utezanje. Moe se pretpostaviti da na sorpciju odluujue djeluju i sekundarne promjene u drvu, pri emu se prije svega misli na preobrazbu bjeljike u sr, pri emu se u staninoj stijenci nataloe niskomolekularne tvari i zauzmu mjesto vezanoj vodi. Posljedica toga je po pravilu nia ravnotena vlanost sri bjeljike iste vrste drva. Tablica 2.3.1. Usporedna tablica udjela ekstraktiva i sorpcijskih svojstava nekih vrsta drva (prema Wangaardu i sur., 1967. te Gorieku, 1992) Vrsta drvaUdjel ekstraktiva (%)Ravnotena vlaga (%) pri SYMBOL 106 \f "GreekMathSymbols"=90% za vrijeme desorpcijeAbies alba 2,83mokra sr bjeljika19,3 1 19,6 1Couraturi pulchra2,88neekstrahirano ekstrahirano21,97 22,67Jacaranda copaia5,93neekstrahirano ekstrahirano24,03 25,14Chlorophora tinctoria17,05neekstrahirano ekstrahirano17,32 24,081Podaci pri SYMBOL 106 \f "GreekMathSymbols"=88% WIEDENBECK i sur. (1990) navode da se ravnotena vlanost borovine s nadmorskom visinom smanjuje, to pripisuju veem udjelu higroskopnih polioza u drvu nie nadmorske visine i veem udjelu ekstraktivnih tvari u drvu viih nadmorskih visina. BOSSHARD (1974) to objanjava veom lignifikacijom zbog jaeg ultraljubiastog zraenja na viim nadmorskim visinama. 2.4. UTJECAJ TEMPERATURE NA SVOJSTVA DRVA 2.4.1. Kemijske promjene Govorei o utjecaju temperature na kemijska svojstva drva misli se na promjene celuloze, polioza i lignina kao njegovih glavnih sastojaka. No pritom se ne smije zanemariti ni vaan utjecaj ekstraktiva sadraj i sastav kojih je razliit u bjeljici i sri. Pod utjecajem temperature nastaje depolimerizacija drvnih komponenata i stvaraju se niskomolekularne topive tvari (slika 2.4.1). Parenjem na atmosferskom tlaku postie se uinak blage hidrolize, koji, kataliziran prirodnim kiselinama iz drva, s povienjem temperature i trajanja izlaganja postaje sve jai (FENGEL, WEGENER, 1984). Ugljikohidratni dio drva, a osobito hemicelulozni sastojci, izrazito su podloni hidrolizi i zato se relativno brzo razgrauju, ve nakon 4 do 20 sati parenja (THOMPSON, 1969). FENGEL i WEGENER (1984) opazili su da u odreenim uvjetima prve promjene nastaju ve pri temperaturi od 100 SYMBOL 176 \f "GreekMathSymbols"C. Oni smatraju da se najvjerojatnije razgrauju O-acetil skupine te da one imaju vaan utjecaj na toplinsku stabilnost polioza. Zagrijavanje drva od 100 do 105 SYMBOL 176 \f "GreekMathSymbols"C uzrokuje isparavanje higroskopski vezane vode, a s produljenjem vremena izlaganja oslobaa se konstitucijska voda visokopolimernih ugljikohidrata, a na osloboenim se mjestima stvaraju novi mostovi. Dovoenje energije i povienje temperature utjee na stalno i sve vee smanjenje hlapljivih i izluujuih sastojaka, to se opaa po smanjenju mase, tj. teine drva (slika 2.4.1). EMBED Excel.Chart.5 \s \* mergeformat Slika 2.4.1. Smanjenje mase drva smreke (Picea abies) nakon obrade razliitim temperaturama u trajanju 24 sata (Fengel i Wegener, 1984, str. 319) Promjene koje su posljedica obrade drva povienom temperaturom u svjeem su drvu u usporedbi s osuenim nekoliko puta bre. Razgradnja brzo napreduje s poveanjem temperature (HILLIS, 1984). Sirovo se drvo spontano razgrauje ak i pri sobnoj temperaturi, iako vrlo sporo, a jae se razgrauju listae nego etinjae, vjerojatno zbog O-acetil grupa koje oslobaaju octenu kiselinu to katalizira daljnje oslobaanje kiseline i pridonosi broj razgradnji drva (HILLIS 1975). Gubitak drvne tvari pri obradi vruom vodom pokazuje da je brzina reakcije toplinske razgradnje drva u vodi mnogo vea nego pri obradi suhog drva suhim ugrijanim zrakom. Gubitak drvne tvari obradom vruom vodom gotovo je jednakog reda veliine kao i pri parenju prosuenog drva na jednakoj temperaturi (NOACK, 1969). TEICHGRSYMBOL 196 \f "Courier New CE"BER (1966) zabiljeio je gubitak drvne tvari tijekom parenja bukovine ve pri 100 SYMBOL 176 \f "GreekMathSymbols"C. Drvna se tvar vjerojatno gubi zbog razgradnje i ispiranja (izluivanja) ekstraktiva i ugljikohidrata. Kemijske analize drva nakon njegova izlaganja toplinskoj obradi pri razliitim temperaturama pokazuju relativno dobru stabilnost glavnih sastojaka sve do 100 SYMBOL 176 \f "GreekMathSymbols"C i do trajanja od 48 sati (slika 2.4.2). Pri viim temperaturama sve se vie smanjuje sadraj polisaharida (holoceluloze), jer su polioze oito osjetljivije na temperaturu nego celuloza. EMBED Excel.Chart.5 \s \* mergeformat Slika 2.4.2. Udjel sastojaka drva bora (Pinus sylvestris) nakon obrade razliitim temperaturama u trajanju 48 sati (Kollmann i Fengel, 1965) Ipak je FENGEL (1967) opazio da ve pri 100SYMBOL 176 \f "Courier New CE"C nastaju strukturne i kemijske promjene celuloze smreke (Picea abies Karst.). Alfa celuloza etinjaa sadri relativno visoke koliine polioza i ostatke lignina. Smanjenje alfa celuloze koje poinje pri 100 SYMBOL 176 \f "GreekMathSymbols"C moe se reducirati gubitkom tih prateih sastojaka tako da sadraj iste celuloze ostane stalan sve do 150 SYMBOL 176 \f "GreekMathSymbols"C, ak i u etinjaa. Sadraj lignina takoer ostane stalan sve do 140-150 SYMBOL 176 \f "GreekMathSymbols"C (FENGEL i WEGENER, 1984). FENGEL (1966b) ustanovio je da sadraj ukupnih polioza u etinjaa vrlo malo pada sve do 180 SYMBOL 176 \f "GreekMathSymbols"C ili ak raste, posebice iznad 180 SYMBOL 176 \f "GreekMathSymbols"C u smrekovini. Odreenje razliitih frakcija polioza (polioze A, polioze B, pentozani) pokazuje da na sadraj polioza posebice utjee razgradnja pentozana i dodatak alkalno topljive celuloze stvorene toplinski uzrokovanim kidanjem lanca (slika 2.4.3). EMBED Excel.Chart.5 \s \* mergeformat Slika 2.4.3. Udjel sadraja polioza u drvu smreke (Picea abies) nakon razliitih temperatura obrade u trajanju 24 sata (Kollmann i sur., 1969) Pod utjecajem toplinske hidrolize u kiselom se mediju najprije i najvidljivije razgrauju poliuronidi, te pentozani u pentoze (ponajprije u ksilozu i arabinozu), a prisutne organske kiseline (octena i maravlja) kataliziraju daljnju razgradnju do stvaranja furfurala (RUNKEL, 1951, RUNKEL i WILKE, 1951). Utjecaj hidrolize oituje se i u kidanju ligninsko-ugljikohidratnih veza koje mijenjaju lignin u bre reagirajui sastojak, oslobaaju se polioze. Postignute frakcije monolignola i oligolignola, koje su rezultat hidrolize eterskih i esterskih veza, dio pentozana i drugih ligninsko-polisaharidnih dijelova se izlue (KSYMBOL 220 \f "Courier New CE"RSCHNER i MALCER, 1965). Poveanje sadraja polioza nakon toplinske obrade drva posljedica je kidanja celuloznog lanca na krae lance. To znai da je prvi korak toplinske razgradnje celuloze kidanje makromolekula i proizvodnja alkalno toplivih proizvoda. Ali stupanj polimerizacije preostale celuloze takoer je smanjen (FENGEL i WEGENER, 1984). Toplinski obraena izolirana celuloza imala je smanjen stupanj polimerizacije (DP) ak pri 100 SYMBOL 176 \f "GreekMathSymbols"C, iako je grijanje trajalo samo 20 minuta (ROFFAEL i SCHALLER 1971). Isti su autori primijetili poveanje stupnja kristaliniteta u toplinski obraenoj celulozi sve do temperatura 120-160 SYMBOL 176 \f "GreekMathSymbols"C, nakon ega slijedi pad. Na stupanj razgradnje i kristaliniteta utjee sadraj vode. Na temperaturama viim od 200 SYMBOL 176 \f "GreekMathSymbols"C zbiva se brza toplinska razgradnja celuloze i stvaraju se hlapivi proizvodi (FENGEL i WEGENER, 1984). Iako se ini da je lignin toplinski najstabilnija komponenta drva, ipak su primijeene razliite promjene ak pri temperaturama niim od 200 SYMBOL 176 \f "GreekMathSymbols"C (KOLLMANN i FENGEL, 1965; FENGEL i PRZYKLENK, 1970). Tako su SOLSYMBOL 193 \f "Courier New CE"R i MELCER (1992) primijetili promjene u ligninu dobivenom iz hidrotermiki obraene hrastovine ve pri 120 SYMBOL 176 \f "GreekMathSymbols"C. Temperatura omekanja lignina ovisi o vrsti izolacije koja mu odreuje kemijsku strukturu (FENGEL i WEGENER 1984). Daljnji kriterij koji utjee na temperaturu omekanja lignina jest molekularna veliina i sadraj vode uzorka (GORING, 1963, prema HILLISU, 1975). Pregled temperatura omekanja glavnih sastojaka drva dan je u tablici 2.4.1. U inertnom mediju piroliza hemiceluloza poinje pri 220SYMBOL 176 \f "Courier New CE"C, pri 280-300SYMBOL 176 \f "Courier New CE"C piroliziraju lignini, a celuloza pirolizira pri 315SYMBOL 176 \f "Courier New CE"C. U prisutnosti zraka toplinska razgradnja zapoinje pri niim temperaturama (180SYMBOL 176 \f "Courier New CE"C i nie) (HILLIS 1975). Tablica 2.4.1. Temperature omekanja glavnih sastojaka drva u suhom i vlanom stanju (Goring, 1963, prema Hillisu, 1975) TvarVlanost (%)Temperatura omekanja (SYMBOL 176 \f "GreekMathSymbols"C)lignin0127-193lignin7-1372-128hemiceluloza0167-181hemiceluloza20-3054-56celuloza0231-244celuloza12-16231-244 Osim glavnih sastojaka staninih stijenki, postoje mnoge tvari koje zovemo akcesornim ili ekstraktivnim tvarima drva. Iako je njihov udjel u drvnoj masi malen (samo nekoliko postotaka) one mogu znatno utjecati na svojstva drva. Za potrebe kemijske analize drva ekstraktivi se izoliraju iz drva razliitim postupcima ekstrakcije, od kojih su destilacija parom i ekstrakcija vodom vrlo slini parenju drva pa se moe pretpostaviti da su ekstrakti dobiveni na taj nain kvalitativno slini tvarima izluenim pri parenju drva. EkstrakcijaGlavne skupinePodskupinePojedinane tvariDestilacija paromSYMBOL 190 \f "GreekMathSymbols"TerpeniSYMBOL 190 \f "GreekMathSymbols"MonoterpeniSYMBOL 190 \f "GreekMathSymbols"kampfenSYMBOL 195 \f "MS LineDraw"fenoliSYMBOL 195 \f "MS LineDraw"seskviterpenikarenSYMBOL 195 \f "MS LineDraw"ugljikohidratiSYMBOL 195 \f "MS LineDraw"diterpenilimonenSYMBOL 195 \f "MS LineDraw"lignaniSYMBOL 195 \f "MS LineDraw"triterpenipinenSYMBOL 195 \f "MS LineDraw"tetraterpeniborneolSYMBOL 195 \f "MS LineDraw"politerpeniVodomSYMBOL 190 \f "GreekMathSymbols"UgljikovodiciSYMBOL 190 \f "GreekMathSymbols"MonosaharidiSYMBOL 190 \f "GreekMathSymbols"arabinozaSYMBOL 195 \f "MS LineDraw"bjelanevineSYMBOL 195 \f "MS LineDraw"krobgalaktozaSYMBOL 195 \f "MS LineDraw"alkaloidiSYMBOL 195 \f "MS LineDraw"pektinske tvarirafinozaNeorganske tvariSYMBOL 190 \f "GreekMathSymbols"KationiSYMBOL 190 \f "GreekMathSymbols"Ca, K, Mg, Na, FeSYMBOL 195 \f "MS LineDraw"Anioni Slika 2.4.4. Pregled skupina ekstraktiva s podskupinama i pojedinanim sastojcima ekstrahiranim parom i vodom (FENGEL i WEGENER, 1984) FENGEL (1966a) je nakon 24 - satne toplinske obrade drva smreke (Picea abies Karst.) ustanovio da se udjel vodotopljivih ekstraktiva poveava s porastom temperature obrade (slika 2.4.5). Na temelju toga zakljuio je da se konverzija polisaharida u hlapljive tvari zbiva u dva stupnja. Prvi je djelomino rastavljanje dugakih lanaca na krae, to se zamjeuje po porastu vodotopljivog dijela. Drugi je stupanj ili neposredna razgradnja kratkih lanaca u monosaharide, uz istodobnu daljnju razgradnju u hlapljive tvari, ili se oligosaharidi raspadaju tako brzo da se meustupnjevi ne mogu ustanoviti. Kako u hladnom vodenom ekstraktu nije pronaao monosaharide, Fengel (1966a) je zakljuio da su meuproizvodi za stvaranje niskomolekularnih razgradbenih proizvoda radikali koji se stvaraju nehidrolitikim pucanjem glikozidnih veza. Prema tome, finalni su produkti toplinske razgradnje metanol, octena kiselina i hlapljivi heterocikliki sastojci. EMBED Excel.Chart.5 \s \* mergeformat Slika 2.4.5. Udjeli ekstraktiva nakon vrue i hladne ekstrakcije pri razliitim temperaturama obraene smrekovine (Picea abies) u trajanju 24 sata (Kollmann et al. 1969) Neki smolnati ekstraktivi mogu zagrijavanjem omekati i prolaskom kroz staninu upljinu prekriti jaice i usporiti ili na druge naine sprijeiti kretanje vlage. Drugi se ekstraktivi mogu promijeniti pod utjecajem topline i blago kiselih uvjeta. Tako leukoantocianini mogu kondenzirati u termostabilne polimere, pa je poveanje brzine suenja zbog parenja drva Notofagus fusca (KININMONTH, 1971, prema HILLISU, 1975) objanjeno upravo toplinskom stabilizacijom elagitanina, kojim je to drvo bogato. Ekstraktivi smreke (Picea glauca) slue kao katalizatori za oksidaciju celuloze ili drva kada se osueni uzorci griju. Pri 120SYMBOL 176 \f "Courier New CE"C i na zraku nastaje jaka oksidacija povrine drva za 70 minuta. S aceton-ekstrahiranim drvom to se zbiva u roku 190 minuta, a s drvom bez ekstraktiva za 200 minuta i pri 160SYMBOL 176 \f "Courier New CE"C (HILLIS, 1975). Osim tih oksidacijskih promjena postoje i druge promjene koje nastaju zbog acetilnih skupina u hemicelulozama. Listae sadre priblino 5% acetilnih skupina, dok ih etinjae sadre oko 2-5%, a koliina osloboenih ovisi o uvjetima okoline. Za vrijeme izlaganja drva visokoj temperaturi, onoj od oko 115 SYMBOL 176 \f "GreekMathSymbols"C (kakva se primjenjuje pri suenja drva visokom temperaturom), moe se osloboditi 1% (listae) odnosno 0,5% (etinjae) octene kiseline propraunato na temelju suhe mase drva (HILLIS 1975). Za vrijeme parenja bukovine i jasenovine zabiljeen je pad pH - vrijednosti kondenzata s vrijednosti 5,5 na priblino 4,5 u roku dva sata (KOLLMANN, 1939). Prema pH - vrijednosti kondenzata uglavnom se moe odrediti i stupanj hidrolize (SANDERMANN i ROTHKAMM, 1959). 2.4.2. Strukturne i morfoloke promjene Morfoloka zapaanja submikroskopskih promjena vana su zato to nam, uz poznavanje kemijskih procesa, pomau da shvatimo makroskopske promjene za vrijeme i nakon termike obrade. U drvu su kemijskom utjecaju najizloeniji unutarnji slojevi stanine stijenke. Unutarnji bradaviasti sloj prilino je otporan na djelovanje kiselina i luina iako je poznato da octena kiselina, koja se stvara u drvu tijekom parenja, razgrauje bradaviasti sloj i djeluje na unutarnji podsloj sekundarnog sloja (S3) (KUBINSKY, 1971). Tu su pojavu takoer opazili KOLLMANN i SACHS (1967) na unutarnjoj strani lanaka traheja bukovine izloene utjecaju poviene temperature. Organske kiseline smanjuju otpornost i stabilnost unutarnjih slojeva stanine stijenke, tako da ve pri parenju poinje bubrenje i smanjenje staninih upljina, to ostaje vidljivo i nakon obrade (KUBINSKI, 1971). Rezultat djelovanja viih temperatura je toplinska razgradnja i gubitak mase. Smanjenje mase pri parenju odraava se poveanim volumnim utezanjem, koje je takoer posljedica mehanikih i submikroskopskih promjena stanine stijenke (FENGEL i WEGENER, 1984). Posljedica razlika u utezanju je poveanje tlanih naprezanja u staninoj stijenci i pojava pukotina. KOLLMANN i sur. (1969) navode da nastale promjene nisu ravnomjerno rasporeene nego ovise o rasporedu i orijentaciji komponenata u pojedinanim slojevima stijenki. Sekundarni se sloj zbog svoje grae utee jae od sastavljene srednje lamele, zato se pri prekoraenju vlane vrstoe stijenke meusobno razdvajaju. Pomnim pregledom pri veim poveanjima mogue je zamijetiti da vanjski sloj sekundarne stijenke (S1) ostane prilijepljen za srednju lamelu, a odvaja se srednji podsloj sekundarnog sloja (S2). Pukotine izmeu vanjskoga i srednjeg sloja sekundarnog podsloja najprije se opaaju na krajevima stanica, gdje je i utezanje izrazitije. Uzrok nastalih pukotina su razliiti smjerovi vlakana i s tim povezana anizotropija utezanja. Kada susjedni svenji mikrofibrila spuznu jedan preko drugoga, u nastaloj pukotini jo ostane dio fibrilnih mostova. Pri daljnjem utezanju fibrilne veze puknu, a pukotina se rairi u smjeru stanine stijenke. U ranom drvu nastaju i pukotine u kutovima stanica, no u kasnom drvu ta je pojava izrazitija. NICHOLAS i THOMAS (1968) navode da su fibrili marga fleksibilniji u parenome materijalu, to temelje na mikroskopskom istraivanju. Na rubu torusa nisu opazili odignute mikrofibrile, koji su sasvim uobiajeni u neparenom drvu, u kojem su rezultat manje fleksibilnosti i koritavosti uvuenih torusa. U neparenome materijalu veina je jaica vrsto zatvorena s nevidljivim otvorom izmeu torusa i nadsvoenja. U parenom drvu jaice su otvorene, a torus raslojen u tri sloja. 2.4.3. Dimenzijska stabilizacija Meu najneugodnija svojstva drva svakako se ubraja njegovo higroskopsko utezanje i bubrenje, koje je posljedica otputanja ili primanja higroskopski vezane vode u higroskopskom podruju od apsolutne suhoe do zasienja staninih vlakana. Razlike u higroskopnosti koje se oituju razliitim ravnotenim vlanostima, utezanju i bubrenju, te u toki zasienja staninih stijenki posljedica su varijabilnosti grae drvne tvari (stanine stijenke), higroskopskog potencijala i anatomske grae pa i naina prerade drva. Meu glavnim drvnim sastojcima najvei kapacitet sorpcije imaju polioze, zatim celuloza, pa lignin. Zbog veeg udjela u drvu, skupnoj sorpciji najvie pridonosi celuloza (47 %), zatim polioze (37 %), a najmanje lignin (16 %) (CHRISTENSEN i KELSEY, 1959). Kao to je ve spomenuto u poglavlju 2.4.1, termika i hidrotermika obrada drva utjeu na prirodu celuloze, polioza, lignina i ekstraktiva, koji lako mijenjaju higroskopnost, stabilnost, difuzivnost ili permeabilnost drva. Postoji mnogo naina dimenzijske stabilizacije drva (npr. KOLLMANN i COTE, 1968). Kontroliranim hidrotermikim postupkom mogu se izazvati kemijski procesi kojima se smanjuju udjeli polioza bez vidljivih utjecaja na smanjenje vrstoe (HILLIS, 1984). Suenje pri visokim relativnim vlanostima zraka smanjuje higroskopnost drva vie nego suenje uz nisku relativnu vlanost zraka, pri emu su za jednak uinak potrebne vie temperature (KININMONTH, 1976). BURMESTER (1973) navodi da vlanosti drva ima vanu ulogu u hidrotermikoj obradi, a optimalna je ona izmeu 20 i 30 %. Mnogi autori navode da se tek iznad 70 SYMBOL 176 \f "GreekMathSymbols"C postiu vidljivi uinci smanjenja higroskopnosti drva (KOLLMANN i FENGEL, 1965; KOLLMANN i sur., 1969; ITOVA, 1970; ESPENAS, 1971; SCHNEIDER, 1973; SMITH, SIAU, 1979; PRICE, KOCH, 1980). SKAAR (1972) objanjava da se iznad 70 SYMBOL 176 \f "GreekMathSymbols"C poveava vibracijska frekvencija, koja smanjuje kohezijske sile, a celulozna se kristalna reetka pone jae njihati, to zajedno s toplinskom dilatacijom povea prostor u njoj i gibljivost vezane vode. Takoer se smanji diferencijalna toplina sorpcije, a to je energija koja se mora dodati toplini isparavanja slobodne vode da bi higroskopski vezana voda isparila iz stanine stijenke. Sve slabije veze meu susjednim celuloznim molekulama smanjuju razlike u vezanju izmeu procesa adsorpcije i desorpcije. Nakon hlaenja celuloza se meusobno jae povee vodikovim vezama, ime se smanji mogunost dodira molekula vode s hidroksilnim skupinama polioza i drvu se smanji mogunost bubrenja i "rada". Jamano je najjednostavniji nain dimenzijske stabilizacije izlaganje drva povienim temperaturama razliitog trajanja, a esto se zaboravlja da je svako tehniko suenje drva na temperaturi vioj od 70 SYMBOL 176 \f "Courier New CE"C vrsta dimenzijske stabilizacije. Uinak poviene temperature na sorpcijska svojstva drva je dvostruk. Ponajprije se oituje trenutanim i reverzibilnim snienjem ravnotene vlage drva pri zadanoj vlanosti zraka. Sekundarni je uinak trajno snienje higroskopnosti, ija jaina ovisi o temperaturi i trajanju izlaganja. Trenutani uinak povienja temperature jest poveanje aktivnosti relativne vlanosti sorbirane vode u drvu kondicioniranome na zadani sadraj vode. Trajno smanjenje ravnotenog sadraja vode drva zbog povienja temperature povezan je s djelominom razgradnjom drvne strukture. Higroskopnost drva uglavnom se smanjuje zbog toplinske razgradnje hemiceluloza koje su najhigroskopniji osnovni sastojak stanine stijenke (STAMM, 1964; iz: SKAAR, 1988, str. 30). Mogue je predvidjeti da e pri viim temperaturama razgraene polioze izlaziti iz stanine stijenke (BURMESTER, 1974). Ako se drvo pari, razgraene se tvari ispiru. Stabilnije komponente tvore meusobno jae kemijske veze i zatvaraju otvore nastale iza difundirajuih polioza. S obzirom na to da polioze imaju najvei sorpcijski kapacitet (CHRISTENSEN, KELSEY, 1959), njihovim se izluenjem povea dimenzijska stabilnost drva. Toplinski obraeno drvo pokazuje vee razlike meu sorpcijskim koeficijentima desorpcije i adsorpcije, a vei su i energijski gubici zavrnog sorpcijskog ciklusa (KOLLMANN i SCHNEIDER, 1963). Rastua temperatura poveava plastifikaciju odnosno smanjuje viskoznost lignina i pektinskih tvari, prije svega u sastavljenoj srednjoj lameli, to moe smanjiti i konano ukloniti sorpcijsku histerezu. TEICHGRABER (1966) opazio je smanjenje higroskopnosti pri otrijim uvjetima parenja. Hildebrand (1966, prema GORIEK, 1987) navodi da se rad drva (tj. bubrenje i utezanje) parenjem bitno ne mijenja. Promjene dimenzija pri adsorpciji parenog drva malo su manje i sporije, a pri desorpciji je utezanje neto vee i bre od utezanja neparenog drva. Prema KOLLMANNU (1969) hidrotermika obrada mnogo jae djeluje na polioze nego na lignin, ime se objenjava i vea dimenzijska stabilnost. Toplina nema znatnijeg utjecaja na diferencijalno bubrenje ni u tangentnom (qT) niti u radijalnom smjeru (qR). Toplinskom obradom borovine poboljaju se samo njezina sorpcijska svojstva (KOLLMANN i SCHNEIDER 1964) (tablica 2.4.2). Tablica 2.4.2. Svojstva bubrenja i sorpcijska svojstva toplinski obraene bjeljike borovine (Pinus sylvestris) (Kollmann i Schneider, 1964) PostupakDiferencijalno bubrenjeSorp. kvoci-jentKoeficijent bubrenjaTang. qT %/%Rad. qR %/%Anizotropija qT/qRRazlika qT-qR %/% s %/%Tang. hT %/%Rad. hR %/%Razlika hT-hR %/%neobraeno0,340,201,20,140,180,0630,0370,026150 SYMBOL 176 \f "GreekMathSymbols"C(6h)0,340,201,70,140,170,0580,0340,024150 SYMBOL 176 \f "GreekMathSymbols"C(24h)0,340,201,70,140,140,0470,0280,019150 SYMBOL 176 \f "GreekMathSymbols"C(48h)0,340,201,70,140,120,0420,0250,017 KUBINSKY je (1971) je nakon parenja svjee hrastovine zapazio poveano linearno i volumno utezanje. Orijentacija fibrila u razliitim slojevima stanine stijenke je takva da jedna drugoj sprijeava maksimalno utezanje odnosno bubrenje. Za vrijeme parenja oslobaa se octena kiselina i utjee na unutranje utezanje odnosno bubrenje. Poveanje utezanja nakon parenja moemo manje pripisati i gubitku ekstraktivnih tvari. WANGAARD i GRANADOS (1967) ustanovili su da u podruju viih relativnih vlanosti srne tvari potisnu sorpcijsku izotermu na dolje. Zagrijavanje pri 70 SYMBOL 176 \f "GreekMathSymbols"C u trajanju do 48 sati ne utjee na sorpcijska svojstva drva tako da ravnotene vlanosti ostanu jednake kao u neobraenom drvu. Vie temperature potisnu sorpcijsku izotermu nadolje (vie u procesu adsorpcije nego u procesu desorpcije), tako da se snize ravnotene vlanosti, to vie, to je hidrotermika obrada dua. Uzroci nastalih promjena najvjerojatnije su posljedica kemijskih reakcija celuloze, polioza i lignina, te razliita hidrofilna i hidrofobna svojstva nakon hidrotermike obrade. Toplinske promjene poinju pri temperaturi 70 SYMBOL 176 \f "GreekMathSymbols"C, iako su do 100 SYMBOL 176 \f "GreekMathSymbols"C vrlo slabe, i preteno se oituju smanjenjem sadraja hidrofilnih polioza, a djelomino se razgradi i depolimerizira i celuloza. Udjel lignina se u jednakoj masi povea, to se mora odraziti na manji sorpcijski kapacitet drva (KOLLMANN i sur. 1969). 2.4.4. Promjena boje KOLLMANN i sur. (1969) su ve kod uzoraka ugrijanih do 105 SYMBOL 176 \f "GreekMathSymbols"C opazili tamnije obojenu srednju lamelu. Zakljuili su da se za vrijeme hidrotermike obrade u tom dijelu stanine stijenke koncentriraju tvari koje utjeu na promjenu boje. Obojenja se javljaju od izluivanja hidroliziranih i kondenziranih tanina. Pri otrijim uvjetima parenja u hidrolizatu se pojave i fenolne tvari. Boja se moe promijeniti i zbog oksidacijske polimerizacije fenolnih tvari (FREY-WYSLING, BOSSHARD, 1959). Prirodna boja drva potamni radi poviene temperature, jer hidroliziraju pentozani koji uslijed djelovanja organskih kiselina prelaze u furfural. Furfural polimerizira u smekaste smolaste tvari koje su sline bakterijski razgraenom ligninu. 2.5. MIKROSKOPSKA, KEMIJSKA I FIZIKALNA SVOJSTVA JELOVINE OPENITO Obina jela (Abies alba Mill., A. pectinata D.C.) naa je najrasprostranjenija etinjaa ije se drvo zbog svojih dobrih svojstava iroko primjenjuje u drvnoj industriji. Najzastupljenija je vrsta drva etinjaa i osnovna sirovina u proizvodnji graevne stolarije te u graevinarstvu openito. 2.5.1. Mikroskopska graa jelovine Jelovina je poznata kao najjednostavnije graena etinjaa. Izgraena je uglavnom od aksijalnih traheida s udjelom od 90,4%. Ostali dio uglavnom ine jednoredni drvni traci bez traheida trakova, visine 10-25 stanica. Prosjena duljina traheida je 4,3 mm. Srednji promjer lumena traheida ranog drva je 34,6 mm, a kasnog drva 16,2 mm. Prosjena je debljina stijenki u ranom drvu 1,85 mm, a u kasnom drvu 0,45 mm. Prijelaz iz ranog u kasno drvo je postupan. Aksijalni parenhim je rijedak i marginalan.  Slika 2.5.1. Histoloka graa poprenog presjeka drva jele (Abies alba Mill.) uz zonu kambija 2.5.2. Kemijska graa Tablica 2.5.1. Udjeli kemijskih sastojaka u drvu jele (Abies alba) i bora (Pinus sylvestris) (prema WagenfSYMBOL 252 \f "Courier New CE"hr, Scheiber, 1974; 1Fengel i Ludwig, 1989; 2Shortle i Bauch, 1986; 3Fengel i Grosser, 1975). SastojakAbies alba Mill. Pinus sylvestris L. 3celuloza 42,3 %48,79pentozan 11,5 %10,1lignin 28,9 %28,86pepeo 0,8 %pH vrijednost 5,5-6,1ekstraktivi:topljivi u benzol-alkoholu  1,7-2,8 %bjeljika 3,47% sr 5,88%vodotopljivi 1vruom vodom, oko 1,75% hladnom vodom, oko 0,9%fenoli topljivi u etilnom alkoholu 2bjeljika 3,5 mg/g sr 5 mg/g 2.5.3. Fizikalna svojstva Prosjena gustoa jelovine u apsolutno suhom stanju kree se od 320 do 710 kg/m3. Radijalno je utezanje oko 3,8 %, a tangentno oko 7,6 %. SELL i KUERA (1989) izmjerili su za jelovinu prosjene gustoe u apsolutno suhom stanju 400 - 450 kg/m3, diferencijalno radijalno utezanje 0,12 - 0,16 %/%, te diferencijalno tangentno utezanje 0,28 - 0,35 %/%. 3. MATERIJAL I METODE 3.1. PRIPREMA MATERIJALA Za pokus je odabrano pet normalnih, ravnih, zdravih, stabala jele (Abies alba Mill.), bez mokre sri i depresije prirasta. Od svakog je stabla ispiljen po jedan trupi, a od svakog trupia pomno su izraene po dvije etvrtae od bjeljike i po dvije etvrtae od sri, bez kompresijskog drva, poprenog presjeka 50x50 mm i stranica paralelnih s tangentnom odnosno radijalnom ravninom trupia (slika 3.1.1). Sve su povrine izblanjane. Ukupni je broj etvrtaa iznosio 20. Od svake su etvrtae izraena i oznaena etiri usporedna uzorka veliina 50x50x15mm. Po dva su od njih toplinski obraena, a po dva su bila kontrolna (slika 3.1.2). Ukupni broj uzoraka bio je 80. 3.2. METODE Svi su uzorci prirodno prosueni i uravnoteeni u normalnoj klimi, tj. pri temperaturi t=20 SYMBOL 176 \f "GreekMathSymbols"C i relativnoj vlazi zraka SYMBOL 106 \f "GreekMathSymbols"=65%. Polovica usporednih uzoraka parena je u sterilizatoru (autoklavu) pri stalnoj temperaturi od 105 SYMBOL 176 \f "GreekMathSymbols"C tijekom 72 sata. Pokus je izveden na usporednim uzorcima sa dvadeset ponavljanja. Svaki je uzorak imao brojanu oznaku u kojoj je prvi broj znaio broj trupia (1,2,3,4,5), drugi je broj bio oznaka bjeljike (1,3) ili sri (2,4), broj na treemu mjestu znaio je da je uzorak paren kod 105 SYMBOL 176 \f "GreekMathSymbols"C 72 sata (1,3) ili da uzorak nije paren (2,4)(slika 3.1.2).  Slika 3.1.1. Popreni presjek trupia sa ucrtanim poprenim presjecima etvrtaa EMBED CDraw \s \* mergeformat Slika 3.1.2. Slika etvrtae sa ispiljenim i oznaenim uzorcima 3.2.1. Higroskopnost i stabilnost Za odreivanje i usporedbu higroskopnosti i stabilnosti toplinski obraene bjeljike i sri jelovine posluila je metoda koju su ustanovili Noack, Schwab i Bartz (1973), na kojoj se temelji i njemaki standard (DIN 52184, 1979). Na dijagramu toka sorpcijskog pokusa brojevima od 0 do 3 oznaen je redoslijed izlaganja odnosno mjerenja za vrijeme pokusa. Uzorci su pareni (samo polovica njih) nakon poetnog kondicioniranja, dakle nakon izlaganja uvjetima oznaenim slovom A (poetna desorpcija), nakon ega su opet kondicionirani u uvjetima oznaenim slovom A sa slike 3.2.1. EMBED Excel.Chart.5 \s \* mergeformat Slika 3.2.1. Dijagram toka sorpcijskog pokusa Metoda se osniva na pretpostavci gotovo linearnog (kvazilinearnog) odnosa izmeu ravnotene vlanosti drva i relativne vlanosti zraka pri stalnoj temperaturi u podruju relativne vlanosti zraka, priblino izmeu 35 i 85 %. Odnos izmeu bubrenja i vlanosti drva u podruju 7 do 20 % sadraja vode zapravo je priblino linearan (slika 3.2.2). Da bi se odredila sorpcijska svojstva drva spomenutom metodom, sirovi se uzorci najprije uravnotee u normalnoj klimi, tj. pri SYMBOL 106 \f "GreekMathSymbols" = 65 % i t = 20 SYMBOL 176 \f "Arial CE"C. Za to je posluila zatvorena posuda sa zasienom otopinom NaNO2, kao na slici 3.2.3. Nakon toga uzorci se kondicioniraju na gornjoj granici kvazilinearnog podruja, tj. pri priblinoj relativnoj vlanosti zraka od 85 %. Takva se klima postie kod 20 SYMBOL 176 \f "Arial CE"C iznad zasiene otopine ZnSO4. Tada se svi uzorci kondicioniraju na donjoj granici kvazilinearnog podruja sorpcije, tj. na priblino 34 % relativne vlage zraka. Takvi se uvjeti postiu pri 20 SYMBOL 176 \f "Arial CE"C iznad zasiene otopine MgCl2 x 6H2O. Nakon svakog kondicioniranja mjere se mase i duljine uzoraka. Iz izmjerenih vrijednosti izrauna se utezanje prouzroeno suenjem (poetno utezanje), koje je vaan podatak pri suenju drva. Takoer se izrauna i sorpcijski koeficijent (s=SYMBOL 68 \f "GreekMathSymbols"u/ SYMBOL 68 \f "GreekMathSymbols"SYMBOL 106 \f "GreekMathSymbols") kao neposredna brojana vrijednost higroskopnosti drva, koji pokazuje koliko se prosjeno promijeni ravnotena vlanost drva ako se relativna vlanost zraka promijeni za 1 %. Sorpcijski koeficijent ovisi o kemijskom sastavu drva, njegovoj unutarnjoj povrini, sadraju ekstraktiva, osobinama ekstraktiva (hidrofobni ili hidrofilni), kao i o uspjenosti postupaka za poboljanje sorpcijskih svojstava. Dimenzijska stabilnost drva ocijenjena je mjerenjem tangentnoga i radijalnog diferencijalnog bubrenja (qT, qR), tangentnoga i radijalnog koeficijenta bubrenja (hT, hR), njihovim razlikama i omjerima (anizotropija) (qT/qR, hT/hR). Diferencijalno bubrenje (q=SYMBOL 68 \f "GreekMathSymbols"SYMBOL 97 \f "GreekMathSymbols"/SYMBOL 68 \f "GreekMathSymbols"u) u tangentnom i radijalnom smjeru (qT, qR) pokazatelj je postotne promjene lateralnih duljina drva ako se sadraj vode drva promijeni za 1 % (SYMBOL 68 \f "GreekMathSymbols"u=1 %). Poeljno je da drvo ima malo diferencijalno bubrenje u tangentnom smjeru i malu razliku izmeu tangentnoga i radijalnog diferencijalnog bubrenja (qT-qR), jer to znai mali rad drva i istodobno visoku stabilnost oblika. Koeficijent bubrenja (h=SYMBOL 68 \f "GreekMathSymbols"SYMBOL 97 \f "GreekMathSymbols"/SYMBOL 68 \f "GreekMathSymbols"SYMBOL 106 \f "GreekMathSymbols") u tangentnome i radijalnom smjeru pokazuje promjenu duljine drva ako se relativna vlaga zraka promijeni za 1 %. Glede ocjene njegova znaenja, vrijedi isto to i za diferencijalno bubrenje. EMBED Excel.Chart.5 \s \* mergeformat Slika 3.2.2. Odnos izmeu bubrenja i vlanosti drva (Noack, Schwab i Bartz, 1973)  Slika 3.2.3. Zatvorena posuda za uravnoteenje vlage uzoraka drva iznad zasienih otopina soli, s ureajem za strujanje zraka, vlagomjerom i uzorcima. Tablica 3.2.1. Mjerila za ocjenjivanje stabilnosti drva (Noack, Schwab i Bartz 1973) qT (%/%)qT-qR (%/%)qT/qRhT (%/%)hT-hR (%/%)hT/hRs (%/%)Ocjena>0,4>0,2>2,0>0,08>0,04>2,0>0,22nepovoljno0,3-0,40,12-0,21,6-2,00,06-0,080,025-0,041,6-2,00,18-0,22normalno<0,3<0,12<1,6<0,060,015-0,025<1,60,16-0,18povoljno(<0,03)<0,015(<1,3)<0,16vrlo povoljno 4. REZULTATI I DISKUSIJA 4.1. HIGROSKOPNOST Sorpcijska svojstva drva oituju se ponajprije u ravnotenoj vlazi i sorpcijskom koeficijentu. Sa slika 4.1.1, 4.1.2. i 4.1.3. vidljivo je da je ravnotena vlaga u jednakim uvjetima izlaganja uvijek nia u neobraenoj sri nego u neobraenoj bjeljici, to se i pretpostavljalo zbog veeg udjela ekstraktivnih tvari u staninim stijenkama sri. Poznato je da one spreavaju ulazak vode u stanine stijenke (CHOONG, 1969). Razlike su statistiki znaajne (tablice 4.1.2, 4.1.3 i 4.1.4). Podaci SHORTLEA i BAUCHA (1986) za zdrave jele (tablica 2.5.1), pokazuju malo vei udjel fenolnih (hidrofobnih) tvari u sri nego u bjeljici. Pretpostavlja se da su nie ravnotene vlage sri upravo posljedica neto veih koliina tih tvari u sri nego u bjeljici. Taj rezultat dokazuje posljedice osravanja u jele. Time je potvren rezultat istraivanja BAUCHA i sur. (1975), koji su na temelju respiracijske neaktivnosti i nepostojanja kroba ustanovili postojanje sri u jele (Abies alba Mill.). Uvijek nie mase uzoraka nakon parenja potvrdile su gubitak drvne tvari nastao parenjem (tablica 4.1.1), to su zabiljeili i mnogi drugi istraivai (npr. TEICHGRSYMBOL 196 \f "Courier New CE"BER, 1966; NOACK, 1969; KOLLMANN i sur. 1969). Parenjem pri 105 SYMBOL 176 \f "GreekMathSymbols"C u trajanju 72 sata razgradilo se i izluilo prosjeno 2% drvne tvari bjeljike i 1% sri, to se pokazalo statistiki znaajnim. Parenje je znatno snizilo ravnotenu vlagu u bjeljici i u sri. Smanjenje higroskopnosti drva zbog parenja zapazio je i TAICHGRSYMBOL 196 \f "Courier New CE"BER (1966). Kako je poznato da se parenjem pri atmosferskom tlaku postie uinak blage hidrolize koji je kataliziran prirodnim kiselinama osloboenim iz drva (FENGEL, WEGENER, 1984), te da se ve nakon 4 do 20 sati parenja hidroliziraju hemicelulozni sastojci drva bora (THOMPSON 1969), pretpostavlja se da su se parenjem jelovine pri 105 SYMBOL 176 \f "GreekMathSymbols"C za 72 sata djelomino razgradile i isprale hemiceluloze kao najhigroskopniji sastojci staninih stijenki drva. Zato su se, uz gubitak drvne tvari, sorpcijska svojstva bjeljike i sri snizila. Nakon parenja pri 105 SYMBOL 176 \f "GreekMathSymbols"C tijekom 72 sata razlika u ravnotenoj vlazi izmeu bjeljike i sri smanjila se i nije vie bila znaajna samo u gornjem podruju relativne vlage zraka (SYMBOL 106 \f "GreekMathSymbols"=86%). U donjem podruju relativne vlage zraka (SYMBOL 106 \f "GreekMathSymbols"=65% i SYMBOL 106 \f "GreekMathSymbols"=34%) razlike ravnotenih vlaga bjeljike i sri bile su i nakon parenja znaajne. Upravo taj rezultat posredno potvruje veu prisutnost ekstraktiva u sri, koji su parenjem isprani, slino kao pri ekstrakciji drva destilacijom parom. Iz istraivanja WANGAARDA i GRANADOSA (1967) poznato je da je uinak ekstrakcije na sorpcijska svojstva drva vidljiv samo u gornjem podruju relativne vlage zraka, to je vidljivo i iz ovog pokusa (tablice 4.1.2, 4.1.3. i 4.1.4). Tablica 4.1.1. Masa parene i neparene bjeljike i sri jelovine, T-test Masa  N Srednja vrijed-nost (g) Razlika Std. Dev.  Razlika std. dev.  t Stupanj slobode p neparena bjeljika 16,153 1,0658parena bjeljika 20 15,869 0,28370 1,0631 0,01613*** 78,667 19 0,00000neparena sr 15,565 0,95086parena sr 20 15,348 0,21610 0,94193 0,02418*** 39,970 19 0,00000*** znaajna razlika pri p<0,05 EMBED STATISTICAGraph \s \* mergeformat Slika 4.1.1. Vlaga ravnotee neparene i parene bjeljike i sri jelovine pri temperaturi 20 SYMBOL 176 \f "Courier New CE"C i 65%-tnoj relativnoj vlazi zraka. Tablica 4.1.2. T-test ravnotenog sadraja vode za uzorke u paru pri 65%-tnoj relativnoj vlazi zraka.  N Srednja vrijed-nost (%)Razlika sred. vrijed. Std. dev.  Razlika Std. dev.  t  Stupanj slobode  pNeparena bjeljika  14,42 0,1241Neparenasr  20 14,01 0,4081 0,1066 0,1562*** 11,685 19 0,0000Parena bjeljika  13,31 0,1173Parena sr  20 13,40 -0,0934 0,1284 0,1737* -2,405 19 0,0265Neparenabjeljika 14,42 0,1241Parena bjeljika  20 13,31 1,1124 0,1173 0,1477*** 33,682 19 0,0000Neparenasr  14,01 0,1066Parena sr  20 13,40 0,6109 0,1284 0,1220*** 22,385 19 0,0000*** znaajna razlika kod p<0,01; * znaajna razlika kod p<0,05; --- razlika nije znaajna kod p<0,05 EMBED STATISTICAGraph \s \* mergeformat Slika 4.1.2. Vlaga ravnotee neparene i parene bjeljike i sri jelovine pri temperaturi 20 SYMBOL 176 \f "Courier New CE"C i 86%-tnoj relativnoj vlazi zraka. Tablica 4.1.3. T-test ravnotenog sadraja vode za uzorke u paru pri 86%-tnoj relativnoj vlazi zraka.  N Srednja vrijed-nost (%) Razlika sred. vrijed. Std. dev. Razlika std. dev. tStupanj slobode pNeparena bjeljika  20,91 0,18023Neparenasr  20 20,29 0,62492 0,16631 0,20178*** 13,850 19 0,00000Parena bjeljika  19,52 0,18405Parena sr  20 19,58 -0,0595 0,29690 0,37179--- -0,7158 19 0,48279Neparenabjeljika 20,91 0,18023Parena bjeljika  20 19,52 1,3886 0,1840 0,22546*** 27,545 19 0,00000Neparenasr  20,29 0,16631Parena sr  20 19,58 0,70424 0,2969 0,26760*** 11,769 19 0,00000*** znaajna razlika kod p<0,01; --- razlika nije znaajna kod p<0,05 EMBED STATISTICAGraph \s \* mergeformat Slika 4.1.3. Vlaga ravnotee neparene i parene bjeljike i sri jelovine pri temperaturi 20 SYMBOL 176 \f "Courier New CE"C i 34%-tnoj relativnoj vlazi zraka. Tablica 4.1.4. T-test ravnotenog sadraja vode za uzorke u paru pri 34%-tnoj relativnoj vlazi zraka.  N Srednja vrijed-nost (%) Razlika sred. vrijed. Std. dev. Razlika std. dev. tStupanj slobode pNeparena bjeljika  7,95 0,11173Neparenasr  20 7,73 0,22263 0,09004 0,13411*** 7,4242 19 0,00000Parena bjeljika  7,05 0,13318Parena sr  20 7,13 -0,0772 0,09433 0,16149* -2,139 19 0,04560Neparenabjeljika 7,95 0,11173Parena bjeljika  20 7,05 0,90052 0,13318 0,13962*** 28,842 19 0,00000Neparenasr  7,73 0,09004Parena sr  20 7,13 0,60062 0,09433 0,06330*** 42,433 19 0,00000*** znaajna razlika kod p<0,01; * znaajna razlika kod p<0,05; 4.3. STABILNOST Tablica 4.1.5. Svojstva sorpcije i bubrenja bjeljike i sri parene i neparene jelovine Postupak i podrijetlo drvaDiferencijalno bubrenjeSorp. koefici-jentKoeficijent bubrenjaTang. qT (%/%)Rad. qR (%/%)Anizotropija qT/qRRazlika qT-qR (%/%) s (%/%)Tang. hT (%/%)Rad. hR (%/%)Razlika hT-hR (%/%)neparena bjeljika0,3670,1602,3280,2070,2490,0910,0400,052neparena sr0,3720,1482,5660,2240,2420,0900,0360,054parena bjeljika 0,3850,1742,2440,2120,2400,0920,0420,051parena sr 0,3920,1652,4250,2270,2400,0940,0400,055 Podaci o diferencijalnom bubrenju, koeficijentu bubrenja te sorpcijskom koeficijentu uglavnom se slau sa podacima za jelu (Abies alba Mill.) iz literature (npr. GORIEK, 1992). Prema kriterijima NOACKA i sur. (1973) (Tablica 3.2.1), jedino diferencijalno bubrenje jelovine u tangentnom i radijalnom smjeru (qT i qR) pripada razredu normalnih vrijednosti, dok su sva ostala svojstva bubrenja i sorpcije jelovine nepoeljna. Drugim rijeima, jelovina normalno "radi" u klimatskim prilikama koje najee prevladavaju u naoj okolini. S obzirom na to da su za praksu vani pokazatelji bubrenja (q, h, qT/qR i s) izvedeni (izraunani) na temelju ravnotenih vlaga kojih je razlika znaajna ali vrlo malena, razlike izmeu tih podataka za bjeljiku i sr, uglavnom su neznaajne. Iz toga se moe zakljuiti da bjeljika i sr jele (Abies alba Mill.) glede svojstava sorpcije i bubrenja imaju podjednaku uporabnu vrijednost. Vrijednosti nominalne gustoe i gustoe u apsolutno suhom stanju u skladu su s podacima iz literature (SINKOVI, 1994). Gustoa uzoraka sri prirodno je malo manja od gustoe odgovarajuih uzoraka bjeljike, a i godovi su malo iri u uzorcima sri nego u odgovarajuim uzorcima bjeljike (tablica 4.1.7, 4.1.8, 4.1.9. i 4.1.10). Poznato je da bubrenje i utezanje ovise o gustoi drva. to je gustoa drva vea, vee je bubrenje i utezanje, a manja anizotropija utezanja (odnos tangentno/radijalno utezanje). U etinjaa se gustoa smanjuje sa poveanjem irine goda. Iako su razlike u bubrenju izmeu bjeljike i sri malene i uglavnom neznaajne, ipak se moe uoiti ovisnost izraunanih veliina bubrenja i sorpcije (q, h i s) o poloaju uzorka na poprenom presjeku (bjeljika ili sr). Za bjeljiku koja ima malo ue godove, pa zato i malo veu gustou od sri, neznatno je vei koeficijent bubrenja (h) i diferencijalno bubrenje (q), dok je anizotropija bubrenja (qT/qR) neznatno manja nego u sri (tablica 4.1.5.), to se i oekivalo. Parenje jelovine (Abies alba Mill.) pri 105 SYMBOL 176 \f "GreekMathSymbols"C tijekom 72 sata neznatno pobolja (smanji) anizotropiju bubrenja, a linearna bubrenja neznatno povea (tablica 4.1.5), tj. pogora. GORIEK je (1987) u slinim uvjetima dobio sline rezultate za bukovinu, a ovim je pokusom potvreno da to vrijedi i za jelovinu. Iz rezultata KOLLMANNA i SCHNEIDERA (1964) (tablica 2.4.2) mogue je uoiti da sama temperatura do 150 SYMBOL 176 \f "GreekMathSymbols"C ne utjee na diferencijalno bubrenje borovine ni u tangentnom ni u radijalnom smjeru i da se poboljaju samo njezina sorpcijska svojstva. U usporedbi s tim rezultatima, dobiveno neznatno pogoranje diferencijalnog bubrenja i koeficijenta bubrenja, uz istodobno poboljanje sorpcijskog koeficijenta bjeljike i sri jelovine, sasvim je oekujue. I HILDEBRAND (1966) navodi da se "rad" drva (tj. bubrenje i utezanje) parenjem bitno ne mijenja. Tablica 4.1.6. Utezanje u kvazilinearnom podruju (od SYMBOL 106 \f "GreekMathSymbols"=86 % do SYMBOL 106 \f "GreekMathSymbols"=34 %), utezanje zbog suenja te apsolutno utezanje Podrijetlo drva i postupakLinearno utezanje od SYMBOL 106 \f "GreekMathSymbols"=86 % do SYMBOL 106 \f "GreekMathSymbols"=34 %Inicijalno utezanje do SYMBOL 106 \f "GreekMathSymbols"=65 %Maksimalno bubrenjetang. (%)rad. (%)SYMBOL 98 \f "GreekMathSymbols"NT (%)SYMBOL 98 \f "GreekMathSymbols"NR (%)SYMBOL 97 \f "GreekMathSymbols"T (%)SYMBOL 97 \f "GreekMathSymbols"R (%)neparena bjeljika4,321,994,361,659,934,24neparena sr4,261,793,991,429,693,80parena bjeljika 4,352,0610,364,88parena sr 4,421,9710,734,60 Nominalna gustoa (R), koja je neposredan pokazatelj gubitka mase, u jelovine se parenjem na 100 SYMBOL 176 \f "GreekMathSymbols"C tijekom 72 sata smanjila prosjeno za 1 % u odnosu prema neparenim uzorcima (tablice 4.1.7, 4.1.8, 4.1.9. i 4.1.10). Podjednaki gubitak mase zabiljeen je i pri parenju bukovine u slinim uvjetima (GORIEK, 1992). I to je pokazatelj razgradnje i ispiranja drvnih tvari, najvjerojatnije upravo drvnih polioza (hemiceluloza) i ekstraktivnih tvari. Tu je pretpostavku potvrdio i usporedni kemijski pokus ekstrakcije parenih i neparenih uzoraka bjeljike i sri jelovine vruom vodom. Ekstrakcijom vruom vodom dobiven je 1% vei sadraj ekstraktiva u parenim nego u neparenim uzorcima. Zbog malog broja uzoraka i nestandardne metode, ovaj pokus nije prikazan u radu. Tablica 4.1.7. Neparena bjeljika uzorakprosjenar0Rusu65u86u34qTqRhThRqT/qRir. godakg/m3kg/m3%%%%%/%%/%%/%%/%mm1121,94420,81371,18181,5914,4821,047,970,33220,13630,08350,03432,43661141,94422,19372,65180,8114,5020,588,030,32720,13870,07900,03352,35881321,56417,70365,20181,5814,3720,897,930,36710,14150,09150,03522,59511341,56417,91364,78181,1114,3620,927,950,37350,14780,09320,03692,52612121,79384,52340,94200,4114,5720,978,030,32480,12470,08080,03102,60422141,79386,64342,47200,1814,6120,658,070,32540,12660,07870,03062,56972322,17390,04345,71198,9714,5421,088,020,32320,13160,08120,03312,45532342,17399,21353,96194,4714,5221,058,040,31970,13380,08000,03352,38973122,01400,06347,59180,7114,3420,777,880,40910,15010,10140,03722,72643142,01401,25348,34178,9014,4220,747,940,40460,15770,09960,03882,56573321,86405,03351,58180,8614,3520,817,860,40350,16130,10050,04022,50163341,86398,92346,84184,6914,3720,837,850,40180,15750,10030,03932,55194121,42485,25415,48139,5114,3820,967,900,40110,19680,10080,04942,03794141,42491,43419,82142,7414,4421,007,960,41170,19370,10320,04862,12554321,51475,64404,18144,4714,3420,967,880,43490,20270,10940,05102,14574341,51477,25405,03143,7114,3520,947,900,42760,20000,10730,05022,13765121,99443,08388,89164,6814,3621,017,930,33840,18120,08510,04551,86815141,99446,26391,54162,1614,6321,368,220,33650,18010,08510,04551,86815321,71436,80382,47160,4714,0820,687,650,35660,16850,08930,04222,11595341,71433,93383,88164,8414,4521,067,990,31850,16170,08010,04061,9702prosjek1,80426,70372,13173,3414,4220,927,950,36690,15960,09150,03982,3275stdev0,2433,7725,5319,610,120,180,110,04100,02550,01040,00660,2679koef var13,217,916,8611,320,860,861,4111,167015,946811,418216,584111,5123min1,42384,52340,94139,5114,0820,587,650,31850,12470,07870,03061,8681max2,17491,43419,82200,4114,6321,368,220,43490,20270,10940,05102,7264n202020202020202020202020 Tablica 4.1.7. Neparena bjeljika (nastavak) uzoraksqT-qRhT-hRbNTbNRbNT/bNRb86-34Tb86-34Rb86-34T/b86-34RaTaRaT/aR%/%%/%%/%%%%%%%1120,25130,19590,04924,51191,47823,05223,97281,71792,31269,29523,72982,49221140,24140,18850,04554,49911,47883,04243,75921,67872,23949,23983,70982,49061320,24920,22560,05624,52271,52302,96954,32261,76352,451110,04183,93672,55081340,24950,22560,05634,67811,52403,06974,39821,84482,384110,17623,98252,55522120,24880,20010,04984,09351,40062,92273,85381,56062,46949,05923,41402,65352140,24200,19880,04814,07351,45972,79063,75401,53972,43819,08303,49752,59702320,25120,19160,04813,93761,43882,73673,87771,65872,33788,85553,64542,42922340,25010,18590,04653,94081,45942,70023,82081,67932,27528,83953,62542,43823120,24780,25910,06424,61821,48153,11734,75811,86192,555610,81083,86772,79513140,24630,24690,06084,67531,46233,19724,67531,94312,406110,82823,93502,75173320,24900,24220,06034,26851,62232,63124,72952,00282,361410,47164,28152,44573340,24960,24440,06104,44091,54252,87914,72091,96312,404810,47514,10842,54974120,25120,20430,05134,76192,02242,35454,72192,44291,932910,96805,24762,09014140,25080,21800,05474,76292,00162,37954,82292,40192,007911,31665,15682,19454320,25150,23220,05845,09192,11702,40525,09192,51652,023411,71095,34402,19144340,25090,22760,05715,12972,11702,42314,99002,47652,014911,80545,38832,19095120,25140,15730,03953,78151,74282,16984,06162,26361,79438,91264,61021,93325140,25280,15640,03953,86081,80182,14274,06082,26231,79508,91074,65121,91585320,25050,18810,04713,98081,66432,39184,24082,10552,01429,53114,26512,23475340,25140,15690,03943,48211,68442,06733,84232,02531,89728,34784,33051,9277prosjek0,24930,20730,05174,35561,65112,67214,32381,98542,20589,93404,23642,3714stdev0,00300,03080,00760,44770,23820,35720,45290,31690,24391,06050,63340,2700koef var1,204414,848214,686610,278814,424113,369410,474915,961511,055410,675814,951811,3861min0,24140,15640,03943,48211,40062,06733,75401,53971,79438,34783,41401,9158max0,25280,25910,06425,12972,11703,19725,09192,51652,555611,80545,38832,7951n202020202020202020202020 Tablica 4.1.8. Neparena sr uzorakprosjenar0Rusu65u86u34qTqRhThRqT/qRir. godakg/m3kg/m3%%%%%/%%/%%/%%/%mm1222,78420,08368,1333,2614,2120,327,880,37590,14900,08990,03562,52361242,78423,96372,2732,1413,9920,137,710,38030,11210,09080,02683,39151423,21421,11368,7433,1114,1420,297,820,38430,14310,09220,03432,68481443,21424,24372,4732,0813,9520,057,690,37840,13940,08990,03312,71332221,85384,94345,9143,9914,1720,257,850,31530,11630,07520,02772,71082241,85384,83345,4644,6614,0320,127,710,31060,11630,07410,02782,67062421,95388,18346,4943,4913,9520,317,740,33800,12140,08170,02932,78502441,95390,77348,3842,0913,8220,007,650,34080,12560,08100,02982,71313223,85372,71328,8234,0914,1120,317,760,38000,13540,09170,03272,80633243,85373,47328,8233,1713,9520,157,580,37550,14050,09080,03402,67213423,74370,56326,5736,9614,0520,407,720,37830,12550,09230,03063,01373443,74366,97324,5835,8413,8420,077,580,36570,12910,08780,03102,83234222,28424,70368,7131,5214,1120,527,790,39970,16220,09790,03972,46464242,28431,49374,9331,3314,0320,447,710,38540,16210,09440,03972,37724422,37428,38370,3431,8114,0320,447,670,40360,17310,09910,04252,33184442,37429,02370,3731,8613,8720,217,580,40670,17360,09880,04222,34325222,35447,00390,5931,9813,9420,327,700,37490,18420,09100,04472,03465242,35446,07389,5032,2014,0920,517,820,37480,17870,09150,04362,09785422,18443,92386,1236,0314,0420,557,830,38730,18470,09470,04522,09685442,18442,34384,6535,8513,9920,447,800,37760,18430,09180,04482,0496prosjek2,66410,74360,5935,3714,0220,297,730,37170,14780,08980,03582,5656stdev0,7028,1921,884,530,110,170,090,02610,02540,00690,00640,3479koef var26,246,866,0712,810,760,821,177,032717,19687,710517,989513,5606min1,85366,97324,5831,3313,8220,007,580,31060,11210,07410,02682,0346max3,85447,00390,5944,6614,2120,557,880,40670,18470,09910,04523,3915n202020202020202020202020 Tablica 4.1.8. Neparena sr (nastavak) uzoraksqT-qRhT-hRbNTbNRbNT/bNRb86-34Tb86-34Rb86-34T/b86-34RaTaRaT/aR%/%%/%%/%%%%%%%1220,23920,22700,05434,13501,42372,90444,25491,78462,38429,90123,83092,58451240,23880,26820,06404,13671,44462,86354,29661,34433,19619,92973,59592,76141420,23980,24110,05784,11751,47912,78384,35741,71902,53499,98023,83982,59921440,23770,23890,05684,07841,40202,90904,25831,66232,56169,83753,69682,66112220,23850,19900,04743,33931,11982,98213,61931,39972,58578,01303,02842,64592240,23860,19430,04643,42271,08133,16543,56291,40172,54188,18542,96912,75692420,24170,21670,05243,66661,18053,10603,90701,48062,63888,73643,03032,88302440,23760,21520,05113,61081,20363,00003,87161,50452,57338,74783,14502,78153220,24130,24460,05904,00561,18333,38514,34611,64462,64269,71223,31542,92943240,24170,23500,05684,02161,28493,12994,30171,70652,52089,72563,51212,76923420,24390,25270,06164,06411,16163,49864,36441,54222,83009,92523,22513,07743440,24010,23660,05683,94551,18243,33704,16581,56312,66519,61583,14183,06064220,24480,23750,05824,38181,52152,87984,60181,98202,321810,57524,17102,53544240,24480,22330,05474,28431,58032,71104,44441,98042,244210,41114,23272,45974420,24560,23050,05664,40001,69532,59554,66002,11412,204310,61954,56732,32514440,24300,23310,05674,50001,73792,58934,64002,09752,212210,76654,57492,35345220,24280,19060,04633,87691,60612,41394,31652,22851,93709,64074,37972,20125240,24400,19620,04793,82081,68672,26524,34092,16872,00169,55514,53402,10745420,24460,20260,04964,02081,74522,30394,48092,24671,99449,94064,57312,17375440,24310,19340,04704,00321,74522,29384,34352,22671,95079,92304,61702,1492prosjek0,24160,22380,05413,99161,42332,85594,25671,78992,42719,68713,79902,5908stdev0,00260,02210,00530,30600,23410,36500,30190,31200,32260,74720,61120,2984koef var1,08829,85389,79087,667316,446012,77917,093517,428813,29257,713516,088111,5188min0,23760,19060,04633,33931,08132,26523,56291,34431,93708,01302,96912,1074max0,24560,26820,06404,50001,74523,49864,66002,24673,196110,76654,61703,0774n202020202020202020202020 Tablica 4.1.9. Bjeljika parena 72 sata na 105 SYMBOL 176 \f "GreekMathSymbols"C uzorakprosjenar0Rusu65u86u34qTqRhThRqT/qRir. godakg/m3kg/m3%%%%%/%%/%%/%%/%mm1111,94417,03366,79184,7313,2819,586,890,34190,13940,08340,03402,45191131,94419,86368,66184,4213,3519,597,140,34300,15230,08220,03652,25291311,56416,17361,19180,6113,2319,456,970,37650,15430,09040,03702,43981331,56415,99361,42184,5313,3319,617,100,38060,15580,09150,03752,44232111,79386,72339,29197,1713,2719,547,020,34190,14320,08230,03452,38762131,79391,44337,24202,9413,4519,837,210,35040,14600,08500,03542,39932312,17388,81342,44199,6913,2919,417,040,33120,14130,07880,03362,34452332,17392,51345,09200,2213,3819,647,150,34120,14150,08190,03402,41243112,01401,65344,56175,3213,2019,296,920,43060,17110,10240,04072,51723132,01405,58347,97180,2713,3619,437,080,43460,17300,10320,04112,51163311,86403,75347,87178,1913,2019,276,910,41510,17320,09860,04122,39593331,86402,28345,63186,2913,3419,477,040,41840,17390,10000,04162,40574111,42484,16410,73139,0513,2919,457,050,43120,21170,10290,05052,03694131,42488,35414,19143,5213,4219,567,110,42950,20760,10290,04972,06854311,51477,23401,73142,9813,2419,386,960,44970,21650,10730,05172,07754331,51476,73401,62146,9113,3819,517,070,44440,21230,10640,05082,09285111,99439,89381,39166,6313,3919,737,150,35700,19460,08640,04711,83425131,99444,37385,88167,6313,5419,987,350,35840,19540,08710,04751,83435311,71436,86377,52155,9013,3419,587,120,37830,18400,09070,04412,05635331,71438,21381,66164,2812,9719,236,730,35480,18530,08530,04461,9149prosjek1,80426,38368,14174,0613,3119,537,050,38540,17360,09240,04162,2438stdev0,2433,1625,0320,100,120,180,130,04130,02630,00950,00630,2298koef var13,217,786,8011,550,880,941,8910,714615,174510,259915,037510,2411min1,42386,72337,24139,0512,9719,236,730,33120,13940,07880,03361,8342max2,17488,35414,19202,9413,5419,987,350,44970,21650,10730,05172,5172n202020202020202020202020 Tablica 4.1.9. Bjeljika parena 72 sata na 105 SYMBOL 176 \f "GreekMathSymbols"C (nastavak) uzoraksqT-qRhT-hRbNTbNRbNT/bNRb86-34Tb86-34Rb86-34T/b86-34RaTaRaT/aR%/%%/%%/%%%%%%%1110,24390,20250,04944,41212,07752,12373,97281,69802,33989,15234,16152,19931130,23950,19080,04574,35392,09752,07583,91451,81782,15349,15634,33512,11211310,24000,22220,05334,74192,14342,21234,26171,84292,312410,25814,50072,27921330,24050,22470,05414,66192,08542,23554,32171,86482,317510,13664,50542,24992110,24080,19870,04784,51282,12132,12743,91371,72102,27419,39274,19102,24122130,24260,20440,04965,64312,59842,17173,98801,75892,267310,82874,73102,28892310,23800,18990,04524,27661,95962,18243,75701,67972,23689,09094,07912,22872330,24010,19980,04804,43822,01722,20023,89841,69762,29649,30944,05242,29733110,23790,25960,06175,08102,12252,39384,78102,02242,364011,41074,63022,46443130,23750,26150,06215,27582,16262,43964,81612,04252,358011,42284,60832,47883310,23760,24180,05754,86972,22272,19094,62932,04252,266510,76584,78392,25043330,23910,24450,05854,92392,16392,27554,68372,06372,269611,07164,78692,31294110,23860,21950,05245,08302,60211,95354,80292,48201,935111,39105,82501,95554130,23950,22190,05315,34112,66372,00514,80102,44341,964911,41075,82871,95774310,23870,23330,05575,55782,73562,03164,97802,53591,963012,12735,94462,04014330,23930,23210,05555,59222,67572,09004,93312,49601,976412,11375,87742,06115110,24200,16240,03934,20502,48451,69254,10492,32421,76629,44555,38431,75435130,24300,16300,03964,10332,52351,62604,14332,34331,76829,29775,35981,73475310,23970,19430,04664,58182,40191,90764,28172,18171,962510,11245,09051,98655330,24060,16950,04084,13752,32841,77704,05762,20791,83779,37914,97261,8862prosjek0,23990,21180,05084,78962,30942,08564,35202,06332,131510,36374,88242,1390stdev0,00180,02930,00680,50230,25140,21260,40690,29790,20901,05370,62970,2112koef var0,756313,839313,361810,487410,885610,19339,349314,44039,805810,167312,89689,8729min0,23750,16240,03934,10331,95961,62603,75701,67971,76629,09094,05241,7347max0,24390,26150,06215,64312,73562,43964,97802,53592,364012,12735,94462,4788n202020202020202020202020 Tablica 4.1.10. Sr parena 72 sata na 105 SYMBOL 176 \f "GreekMathSymbols"C uzorakprosjenar0Rusu65u86u34qTqRhThRqT/qRir. godakg/m3kg/m3%%%%%/%%/%%/%%/%mm1212,78421,20361,5333,7113,5819,747,220,39960,15760,09620,03802,53461232,78424,79366,7034,4113,5719,567,190,39690,15780,09440,03752,51591413,21432,77365,4033,8213,3120,197,170,42220,17190,10570,04302,45601433,21430,00365,6034,2313,3719,857,110,41040,15860,10060,03892,58842211,85384,85342,9845,2513,3519,187,150,31550,12550,07300,02912,51272231,85386,19343,2946,2213,3919,227,130,32560,12670,07570,02952,56932411,95391,29345,8744,3013,1919,687,070,34330,13480,08320,03272,54762431,95392,38346,0344,9413,3019,287,070,35810,13430,08410,03152,66563213,85371,31324,1534,6213,4819,307,140,39400,14010,09210,03282,81233233,85373,74325,2435,4213,4619,327,070,39370,14810,09280,03492,65763413,74370,23322,6036,8913,3919,667,080,38740,13180,09370,03192,93833433,74367,45320,7837,9713,3719,277,030,39420,14090,09280,03322,79734212,28425,23363,9931,7413,4719,557,150,42480,17420,10130,04152,43854232,28428,45368,2932,8413,4819,517,120,41270,18610,09830,04432,21784412,37436,62362,7732,5713,2820,077,020,44720,19650,11220,04932,27644432,37435,95365,7033,0013,1919,656,980,44020,19510,10730,04752,25655212,35449,03386,6632,2413,2319,316,990,38710,19500,09180,04621,98565232,35447,45385,2033,7113,5619,717,260,38470,19360,09210,04631,98715412,18447,10382,6736,3913,6120,047,360,40870,20690,09970,05051,97495432,18443,84381,3137,5813,4919,637,220,40310,22800,09620,05441,7684prosjek2,66412,99356,3436,5913,4019,597,130,39250,16520,09420,03962,4250stdev0,7029,5121,374,730,130,300,090,03440,03040,00980,00770,3135koef var26,247,156,0012,930,961,521,328,770018,385310,368119,427312,9292min1,85367,45320,7831,7413,1919,186,980,31550,12550,07300,02911,7684max3,85449,03386,6646,2213,6120,197,360,44720,22800,11220,05442,9383n202020202020202020202020 Tablica 4.1.10. Sr parena 72 sata na 105 SYMBOL 176 \f "GreekMathSymbols"C (nastavak) uzoraksqT-qRhT-hRbNTbNRbNT/bNRb86-34Tb86-34Rb86-34T/b86-34RaTaRaT/aR%/%%/%%/%%%%%%%1210,24080,24190,05825,13792,24452,28914,49821,88382,387911,20504,76592,35111230,23790,23920,05694,79332,04652,34214,43381,86602,376110,74984,59602,33891410,25040,25030,06276,01402,84282,11554,89512,12212,306712,29535,46882,24831430,24510,25180,06175,61662,62162,14254,67721,92122,434611,82395,17792,28352210,23140,18990,04393,91841,56092,51033,49861,46092,39498,50333,41472,49022230,23240,19890,04623,92001,59972,45053,62001,47972,44648,69573,49752,48622410,24230,20850,05054,24081,65932,55573,96081,63932,41619,22003,58252,57362430,23470,22370,05254,29121,58382,70943,99041,58382,51959,53223,52842,70153210,23380,25390,05944,75331,64362,89204,33211,64362,635710,55433,61372,92063230,23560,24560,05794,66371,68542,76714,36351,74562,499710,53103,96332,65713410,24200,25550,06184,80291,56063,07754,40261,60062,750610,72463,64992,93833430,23530,25330,05964,68841,58192,96384,36791,66202,628110,42043,73912,78694210,23840,25060,05975,16312,08172,48034,72282,06162,290811,51534,75992,41924230,23820,22660,05405,10102,02242,52224,60092,20262,088811,13834,67412,38304410,25090,25080,06296,48963,21042,02155,15182,41282,135213,27756,25002,12444430,24370,24510,05976,01882,97052,02624,95902,33252,126012,48315,97932,08775210,23700,19220,04554,52272,30411,96294,32262,28411,892510,38225,20661,99405230,23940,19110,04584,45912,31021,93024,33912,29011,894810,37305,24311,97845410,24390,20170,04924,72192,48751,89834,68192,48751,882210,72225,52501,94075430,23870,17520,04184,53002,38521,89924,53002,68591,686610,47395,36431,9525prosjek0,23960,22730,05454,89232,12012,37784,41741,96832,289710,73104,60002,3828stdev0,00540,02700,00700,69110,51780,37420,41320,36720,28731,20330,91250,3144koef var2,244111,897812,798414,126724,424715,73679,353318,654012,547211,213519,836213,1939min0,23140,17520,04183,91841,56061,89833,49861,46091,68668,50333,41471,9407max0,25090,25550,06296,48963,21043,07755,15182,68592,750613,27756,25002,9383n202020202020202020202020 5. ZAKLJUCI 1. Ravnotena vlaga i sorpcijski koeficijent sri pri svim trima uvjetima bili su znaajno nii nego u bjeljici, to fizikalno potvruje proces osravanja (BAUCH et al. 1975). 2. Ravnotena vlaga i sorpcijski koeficijent parenih uzoraka bjeljike i sri bili su znaajno nii nego u odgovarajuih usporednih neparenih uzoraka. Snienje favnotene vlage pripisuje se kemijskom uinku temperature, tj. toplinskoj razgradnji hemiceluloze kao najhigroskopnije komponente stanine stijenke. Pretpostavlja se da uinak razgradnje hemiceluloze premauje uinak izluivanja ekstraktivnih tvari. 3. Razlika izmeu ravnotene vlage parene bjeljike i sri bila je znaajna samo pri niim vlanostima zraka (SYMBOL 106 \f "Symbol"=65% i SYMBOL 106 \f "Symbol"=34%). To pokazuje utjecaj srnih tvari na ravnotenu vlagu, koji je vidljiv samo u gornjem podruju relativne vlage zraka, ime se potvruju istraivanja WANGAARDA i GRANADOSA (1967). 4. Iako znaajne, razlike izmeu ravnotene vlage bjeljike i sri jelovine bile su vrlo malene. Razlike u sorpcijskim svojstvima (s, q, h) izmeu bjeljike i sri kao posljedice razlika njihovih ravnotenih vlaga toliko su malene da nisu bitne za upotrebu jelovine. Glede sorpcijskih svojstava, bjeljika i sr jelovine podjednake su uporabne vrijednosti. 6. SAETAK U pet sluajno izabranih stabala i na 40 uzoraka bjeljike i 40 uzoraka sri obine jele (Abies alba Mill.) odreena je ravnotena vlaga, sorpcijski koeficijent (s), diferencijalno bubrenje (q) i koeficijent bubrenja (h). Polovica usporednih uzoraka parena je pri 105 SYMBOL 176 \f "GreekMathSymbols"C 72 sata. Svi su uzorci izloeni i uravnoteeni u sljedeim uvjetima pri sobnoj temperaturi 20 SYMBOL 176 \f "GreekMathSymbols"C: (A) relativnoj vlazi zraka SYMBOL 106 \f "GreekMathSymbols"=65%, (B) SYMBOL 106 \f "GreekMathSymbols"=86% i (C) SYMBOL 106 \f "GreekMathSymbols"=34%. Nepareni uzorci sri pokazali su znaajno niu ravnotenu vlagu i sorpcijski koeficijent s, to upuuje na proces osravanja. Ravnotena vlaga parenih uzoraka bila je u svim uvjetima (A), (B) i (C) znaajno nia od neparenih. Razlika ravnotene vlage izmeu sri i bjeljike parenih uzoraka bila je znaajna samo u uvjetima (A) i (C). 7. SUMMARY In five randomly selected silver fir (Abies alba Mill.) test trees forty sapwood and forty heartwood samples were taken and EMC, sorption coefficient (s), differential swelling (q), and swelling coefficient (h) were measured. The half of parallel samples were steamed at 105 SYMBOL 176 \f "GreekMathSymbols"C for 72 hours. All treated and untreated samples were exposed to three different climates at room temperature, i.e. 20 SYMBOL 176 \f "GreekMathSymbols"C: (A) relative air humidity (SYMBOL 106 \f "GreekMathSymbols")=65%, (B) SYMBOL 106 \f "GreekMathSymbols"=86% and (C) SYMBOL 106 \f "GreekMathSymbols"=34%. Untreated heartwood samples showed significantly lower EMC and s, which indicates heartwood formation. EMC of steamed samples at all climates (A), (B) and (C), were significantly lower than EMC of unsteamed samples. The differences between steamed heartwood and sapwood samples were significant only at climates (A) and (C). 8. ZAHVALA Usjeajui duboko potovanje i divljenje, veliku zahvalnost na razumijevanju u nesebinoj pomoi upuujem gospodi prof. dr. Boidaru Petriu, prof. dr. Niki Torelliju i doc. dr. Slavku Govorinu. Zahvaljujem takoer Katedri za tehnologiju drva i Drvnotehnolokom odsjeku Biotehnikog fakulteta u Ljubljani to su mi omoguili rad na doktorskoj disertaciji. Takoer zahvaljujem svim suradnicima u Zagrebu i Ljubljani na pruenoj potpori, a posebno ing. Petru Cunderu za preciznu i savjesnu izradu uzoraka, te doc. dr. Radovanu Despotu za pomo u pripremi knjige. 7. LITERATURA BAMBER, R.K., 1976a: Heartwood: Its function and formation. Wood Sci. Tech. 10(1):1-8. BAMBER, R.K., 1976b: Anatomical aspects and the role of heartwood formation. Forestry commission of New South Wales, Australia. BAUCH, J.; BERNDT, H.; 1973: Variability of the chemical composition of the pit membranes in bordered pits of gymnosperms. Wood Sci. Tecnol. 7:6-19. BAUCH, J.; HSYMBOL 214 \f "Courier New CE"LL, W.; ENDEWARD, R.; 1975: Some aspects of wetwood formation in fir. Holzforschung, 29(6): 198-205. BAUCH, J.; LIESE, W.; SCHOLZ, F., 1968: SYMBOL 220 \f "Courier New CE"ber die Entwicklung und stoffliche zusammensetzung der HoftSYMBOL 252 \f "Courier New CE"pfelmembranen von LSYMBOL 228 \f "Courier New CE"ngstracheiden in Coniferen. Holzforschung, 22(5):144-153. BAUCH, J.; SCHWEERS, W.; BERNDT, H., 1974: Lignification during heartwood formation: Comparative study of rays and bordered pit membranes in coniferous woods. Holzforschung, 28(3): 86-91. BLAND, D.E., 1971: The relation of lignin and polyphenol content of tasmanian alpine ash (Eucalyptus delegatensis R.T.Bak.) to shrinkage and recovery. Wood Sci. Technol. 5:17-26. BOSSHARD, H.H., 1974: Holzkunde, Vol. 2. BirkhSYMBOL 228 \f "Courier New CE"user Verlag, Basel und Stuttgart. BOSSHARD, H.H., 1968: On the formation of the facultatively colored heartwood in Beilschmiedia tawa. Wood Sci. Tecnol. 2(1),(1-12). BOSSHARD, H.H., 1966: Notes on the biology of heartwood formation. IAWA News Bull. 1966(1):11-14. BROOKER, R.E., 1989: An explanation for the characteristic appearance of aspirated pits. Abstracts of papers and posters. IAWA-Bull. 1989, 10(3):335. BURMESTER, A., 1973: EinfluSYMBOL 223 \f "Courier New CE" einer WSYMBOL 228 \f "Courier New CE"rme-Druck-behandlung halbtrockener Holzes auf seine Formbestandigkeit. Holz als Roh-und Werkstoff. 31(8):237-243. BURMESTER, A., 1974: VerSYMBOL 228 \f "Courier New CE"nderungen der Darrabmessungen von Holz durch Umlagerung wasserlSYMBOL 246 \f "Courier New CE"slicher Stoffe in der Zellwand. Holz als Roh-und Werkstoff. 32(6): 229-233. CHOONG, E.T. 1969: Effect of extractives on shrinkage and other hygroscopic properties of ten Southern Pine woods. Wood and Fiber. 1(2), (124-33) iz Foresry-Abstracts 1970 031-03280. CHOONG, E.T.; ACHMADI, S.S., 1991: Effect of extractives on moisture sorption and shrinkage in tropical woods. Wood and Fiber Science, 23(2): 185-196. CHOONG, E.T.; FOGG, P.J., 1989: Differences in moisture content and shrinkage between innerwood and outerwood of two shortleaf pine trees. For. Prod. Journ. 39(3): 13-18. CHRISTENSEN, G.N.; KELSEY, K.E., 1959: Die Sorption von Waserdampf durch die chemischen Bestandteile des Holzes. Holz als Roh-und Werkstoff. 17(5): 189-203. DIN 52184, 1979. Testiranje drva; odreivanje bubrenja i utezanja ESPENAS, L.D., 1971: Shrinkage of douglas fir, western hemlock, and red alder as affected by drying conditions. For. Prod. Journ., 21(6): 44-46. FENGEL, D., 1970: Ultrastructural changes during aging of wood cells. Wood Sci. Technol., 4: 176-188. FENGEL, D., 1966a: SYMBOL 220 \f "Courier New CE"ber die VerSYMBOL 228 \f "Courier New CE"nderung des Holzes und seiner Komponenten im Temperaturbereich bis 200SYMBOL 176 \f "Courier New CE"C - Erste Mitteilung: HeiSYMBOL 223 \f "Courier New CE"- und Kaltw      !"#$%&'()*+,-./0123456789:;<=>?@ABCDEFGHIJKLMNOPQRSTUVWXYZ[\]^_`abcdefghijklmnopqrsuvwxyz{|}~asserextrakte von thermisch behandeltem Fichtenholz. Holz als Roh-und Werkstoff. 24(1): 9-14. FENGEL, D., 1966b: SYMBOL 220 \f "Courier New CE"ber die VerSYMBOL 228 \f "Courier New CE"nderung des Holzes und seiner Komponenten im Temperaturbereich bis 200SYMBOL 176 \f "Courier New CE"C - Zweite Mitteilung: Die Hemicellulosen in unbehandeltem und thermisch behandeltem Fichtenholz. Holz als Roh-und Werkstoff. 24(3): 98-109. FENGEL, D., 1967: SYMBOL 220 \f "Courier New CE"ber die VerSYMBOL 228 \f "Courier New CE"nderung des Holzes und seiner Komponenten im Temperaturbereich bis 200SYMBOL 176 \f "Courier New CE"C - Vierte Mitteilung: Das Verhalten der Cellulose im Fichtenholz bei thermischer Behandlung. Holz als Roh-und Werkstoff. 25(3): 102-111. FENGEL, D.; GROSSER, D., 1975: Chemische Zusammensetzung von Nadel- und LaubhSYMBOL 246 \f "Courier New CE"lzern. Holz als Roh-und Werkstoff. 33(1): 32-34. FENGEL, D.; PRZYKLENK, M., 1970: SYMBOL 220 \f "Courier New CE"ber die VerSYMBOL 228 \f "Courier New CE"nderung des Holzes und seiner Komponenten im Temperaturbereich bis 200SYMBOL 176 \f "Courier New CE"C FSYMBOL 252 \f "Courier New CE"nfte Mitteilung: EinfluSYMBOL 223 \f "Courier New CE" einer WSYMBOL 228 \f "Courier New CE"rmebehandlung auf das Lignin in Fichtenholz. Holz als Roh-und Werkstoff. 28(7): 254-263. FENGEL, D.; WEGENER, F., 1984: Wood chemistry, ultrastructure, reactions. Walter de Gruyter, Berlin, 613 str. FREEMAN, R.D., 1946: The chemical analysis of wood. u WISE L.E.: Wood chemistry. str: 553-670. Am. Chem. Soc. Reinhold Publish. Corp. 1946. FREY-WYSSLING, A.; BOSSHARD, H.H., 1959: Citology of the ray cells ni sapwood and heartwood. Holzforschung 13:129-136. GIORDANO, G., 1971: Technologia del legno, Vol. 1. Torino: Unione Tipografico-Editrice GORING, D.A.I., 1963: Thermal softening of lignin, hemicellulose, and cellulose. Pulp and Paper Mag. Can., 64(12): 517-527 (iz HILLISA, 1975) GORIEK, ., 1987: Vpliv parjenja na fizikalne in obdelavostne lastnosti bukovine (Fagus sylvatica L.). Magistrsko delo, Univerza v Ljubljani, Biotehnika fakulteta, Oddelek za lesarstvo GORIEK, ., 1992: Vpliv prene kritvene anizotropije lesa na suenje in stabilnost. Doktorska disertacija, Univerza v Ljubljani, Biotehnika fakulteta, Oddelek za lesarstvo. GROSSER, D., 1977: Die HSYMBOL 246 \f "Courier New CE"lzer Mitteleuropas. Springer-Verlag, Berlin, 208 str. HIGUCHI, T.; ONDA, Y.; FUJIMOTO, Y., 1969: Biochemical aspect of heartwood formation with special reference to the site of biogenesis of heartwood compounds. Wood Res. 48:15. HILLIS, W.E., 1968: Chemical aspects of heartwood formation. Wood Sci. and Tecnol. 2:241-259. HILLIS, W.E., 1987: Heartwood and tree exudates. Berlin: Springer-Verlag. 268. HILLIS, W.E., 1984: High temperature and chemical effects on wood stability. Part 1: General considerations. Wood Sci. Tecnol. 18:281-293. HILLIS, W.E., 1975: The role of wood characteristics in high temperature drying. Journal of the Institute of Wood Science, 7(2): 60-66. HILLIS, W.E., 1971: Distribution, properties and formation of some wood extractives. Wood Sci. Tecnol., 5: 272-289. HUGENTOBLER, U.G., 1965: Zur Cytologie der Kernholzbildung. Vierteljahrsschrift der Naturforschenden Gesellschaft in ZSYMBOL 252 \f "Courier New CE"rich, 110(2): 321-342. IAWA, Committee on nomenclature, 1964: Multilingual glossary of terms used in wood anatomy. Izd. Kurth. Mitt. Schweiz. Anst. Forstl. Versuchsw. 40 (1). JACQUINOT, C.; TRENARD, Y., 1966: Chemical methods of distinguishing heartwood and sapwood in some conifers and hardwoods. Bull. Soc. Bot. France. 113 (5/6),(278-82). iz Forestry-Abstracts 1967 028-04510. KININMONTH, J.A.; 1976: Effect of timber drying temperature on subsequent moisture and dimensional changes. N.Z.J. For. Sci. 6(1):101-107. KININMONTH, J.A., 1971: Effect of steaming on the fine structure of Nothofagus fusca. New Zealand J.For.Sci., 1,129-139. KOLLMANN, F., 1939: VorgSYMBOL 228 \f "Courier New CE"nge und SYMBOL 196 \f "Courier New CE"nderungen von Holzeigenschaften beim DSYMBOL 228 \f "Courier New CE"mpfen. Holz als Roh-und Werkstoff. 2(1): 1-11. KOLLMANN, F.F.; CSYMBOL 212 \f "Courier New CE"TSYMBOL 201 \f "Courier New CE", W.A., 1968: Principles of wood science and technology. p.390. Berlin, Heidelberg, New York: Springer KOLLMANN, F.F.; FENGEL, D., 1965: SYMBOL 196 \f "Courier New CE"derungen der chemischen Zusammensetzung von Holz durch thermische Behandlung. Holz als Roh-und Werkstoff. 23(12): 461-468. KOLLMANN, F.F.; SACHS, I.B., 1967: The effects of elevated temperature on certain wood cells. Wood Sci. Technol. 1:14-25. KOLLMANN, F.; SCHMIDT, E.; KUFNER, M.; FENGEL, D.; SCHNEIDER, A., 1969: GefSYMBOL 252 \f "Courier New CE"ge- und EigenschaftsSYMBOL 228 \f "Courier New CE"nderungen im Holz durch mechanische und thermische Beanspruchung. Holz als Roh-und Werkstoff. 27(11): 407-425. KOLLMANN, F.; SCHNEIDER A., 1963: SYMBOL 220 \f "Courier New CE"ber das Sorptionsverhalten wSYMBOL 228 \f "Courier New CE"rmebehandelter HSYMBOL 246 \f "Courier New CE"lzer. Holz als Roh-und Werkstoff. 21(3): 77-85. KRAHMER, R.L.; CSYMBOL 212 \f "Courier New CE"TSYMBOL 201 \f "Courier New CE", W.A. 1963: Changes in coniferous wood cells associated with heartwood formation. TAPPI, 46(1), 42-49. KRAMER, P.J.; KOZLOWSKI, T.T., 1979: Physiology of trees. McGraw-Hill, New York, 811 str. (iz HILLISA, 1987) KUBINSKY, E., 1971: Die EinfluSYMBOL 223 \f "Courier New CE" des DSYMBOL 228 \f "Courier New CE"mpfens auf die Holzeigenschaften. Holzforschung und Holzverwertung, 23(1): 1-11. KUO, M.L.; ARGANBRIGHT, D.G., 1980a: Cellular distribution of extractives in redwood and incense cedar. Part I. Radial variation in cell-wall extractive content. Holzforschung, 34(1):17-22. KUO, M.L.; ARGANBRIGHT, D.G., 1980b: Cellular distribution of extractives in redwood and incense cedar. Part II. Microscopic observation of the location of cell wall and cell cavitiy extractives. Holzforschung, 34(2):41-47. KUTSCHA, N.P.; SACHS, I.B., 1962: Color tests for differentiating heartwood and sapwood in certain softwood tree species. U.S.For.Prod.Lab. Report No. 2246 iz GEORGE TSOUMIS: SCIENCE AND TECHNOLOGY OF WOOD KUTSCHA, N.P.; SCHWARZMANN, J.M., 1975: The lignification sequence in normal wood of balsam fir. Holzforschung, 29(3): 80-84. KSYMBOL 220 \f "Courier New CE"RSCHNER, K.; MALCER, A., 1965: SYMBOL 220 \f "Courier New CE"ber die chemischen verSYMBOL 228 \f "Courier New CE"nderungen des Buchenholzes bei thermischer Behandlung. Holzforschung, 19(6):161-178. LIESE, W.; BAUCH, J., 1967: On the closure of bordered pits in conifers. Wood Sci. and Technol. 1:1-13. NEESANSYMBOL 221 \f "Courier New CE", V., 1966: Die Vitalitatsveranderung der Prenchymzellen als physiologische Grundlage der Kernholzbildung. Holzforschung und Holzverwertung 18: 4, 61-65. NEESANSYMBOL 221 \f "Courier New CE", V., 1968: The biophysical characteristics of two tipes of heartwood formation in Quercus cerris L. Holzforschung und Holzverwertung 20:3, 49-52. NICHOLAS, D.D.; THOMAS, R.J., 1968: Influence of steaming on ultrastructure of bordered pit membrane in loblolly pine. For. Prod. Journ., 18(1):57-59. NOACK, D., 1969: SYMBOL 220 \f "Courier New CE"ber die HeiSYMBOL 223 \f "Courier New CE"wasserberandlung von Rotbuchenholz im temperaturbereich von 100 bis 180 SYMBOL 176 \f "Courier New CE"C. Holzforschung und Holzverwertung 21(5):118-123 NOACK, D.; SCHWAB, E.; BARTZ, A., 1973: Characteristics for judgment of the sorption and swelling behaviour of wood. Wood Sci. Tecnol., Vol 7 (1973): 218-236 NOBUCHI, T.; TAKAI, K.; HARADA, H., 1987: Distribution of heartwood phenols in the trunk of sugi (Cryptomeria japonica D.Don) and partial characterization of heartwood formation. Mokuzai Gakkaishi, 33(2): 88-96. PANDALAI, R.C.; NAIR, G.M.; SHAH, J.J., 1985: Ultrastructure of ray parenchyma cells in the wood of Melia azedarach L. (Meliaceae). Wood Sci. Tech. 19:201-209. PARAMESWARAN, N.; BAUCH, J., 1975: On the origin of phenolic compounds in the wood rays of Abies alba. Wood Sci. Technol. 9: 165-173. PETRI, B., 1971: Utjecaj strukture drva na permeabilnost etinjaa. umarski list, 95, 5-6:125-141. PETRI, B., 1972: Utjecaj strukture drva na permeabilnost listaa. umarski list, 96, 9-10:364-376. PHILLIPS, E.W.J., 1933: Movement of the pit membrane in coniferous woods with special reference to preservative treatmet. Forestry, Vol.7, No.2, 109-120. PRICE, E.; KOCH, P., 1980: Kiln temperature affect shrinkage, warp, and mechanical properties of southern pine lumber. For. prod. Journ., 30(8): 41-47. POPPER, R.; BOSSHARD, H.H., 1976: Calorimetric measurements for determination of differences in cellulose-lignin system of compression wood and normal wood. Holz als Roh-und Werkstoff. 34:8,281-288. ROAFEL, E.; SCHALLER, K., 1971: EinfluSYMBOL 223 \f "Courier New CE" thermischer Behandlung auf Cellulose. Holz als Roh-und Werkstoff. 29(7): 275-278. RUNKEL, R.O.H., 1951: Zur Kenntnis des thermoplastichen Verhaltens von Holz, I. Holz als Roh-und Werkstoff. 9(2):41-53. RUNKEL, R.O.H.; WILKE, K.D., 1951: Zur Kenntnis des thermoplastichen Verhaltens von Holz, II. Holz als Roh-und Werkstoff. 9(7):260-270. SALAMON, M.; KOZAK, A., 1968: Shrinkage of sapwood and heartwood of young Douglas-Fir trees. For. Prod. J. 18(3),(90-4). SANDERMANN, W.; ROTHKAM, M., 1959: SYMBOL 220 \f "Courier New CE"ber die Bestimmung der pH-Werte von HandelshSYMBOL 246 \f "Courier New CE"lzern und deren Bedeutung fSYMBOL 252 \f "Courier New CE"r die Praxis. Holz als Roh-und Werkstoff. 17(11): 433-440. SCHNEIDER, A., 1973: Zur Konvektionstrocknung von Schnittholz bei extrem Temperaturen. Zweite Mitteilung. Holz als Roh-und Werkstoff. 31: 198-206. SCHWEINGRUBER, F., 1978: Mikroskopische aholzanatomie. EidgenSYMBOL 246 \f "Courier New CE"sische Anstalt fSYMBOL 252 \f "Courier New CE"r das forstliche Versuchswesen, Birmensdorf, Komissionsverlag, ZSYMBOL 252 \f "Courier New CE"rcher SCHWEINGRUBER, F., 1990: Anatomie europSYMBOL 228 \f "Courier New CE"ischer HSYMBOL 246 \f "Courier New CE"lzer - Anatomy of European woods. Forschungsanstalt fSYMBOL 252 \f "Courier New CE"r Wald, Schnee und Landschaft, Birmensdorf (Hrsg.). Haupt, Bern und Stuttgart. SELL, J.; KUERA, L. 1989: Schweizer Weistannenholz. Holz als Roh-und Werkstoff. 47: 463-469. SEHLSTEDT-PERSSON, S.M.B., 1995: High-temperature drying of Scots pine. A comparison between HT- and LT-drying. Holz als Roh- und Werkstoff, 53: 95-99. SHIGO, A.L.; HILLIS, W.E., 1973: Heartwood, discolored wood, and microorganisms in living trees. Ann. Rev. Phytopathol. 11:197-222. SHIGO, A.L., 1986: A new tree biology dictionary. Shigo and trees, Associates, Durham, NH, pp. 132. SHORTLE, W.C.; BAUCH, J., 1986: Wood characteristics of Abies balsamea in New England states compared to Abies alba from sites in Europe with decline problems. IAWA Bull. 7(4):375-387. SINKOVI, T., 1994: Fizika i mehanika svojstva juvenilnog drva jele (Abies alba Mill.) iz Gorskog Kotara. Magistarski rad. umarski fakultet sveuilita u Zagrebu. SKAAR, C., 1972: Water in wood. Syracuse univ. press, 218 str. SKAAR, C., 1988: Wood-water relations. Springer-Verlag, Berlin, 283 str. SMITH, W.B.; SIAU, J.F., 1979: High temperature drying of red pine. Journal of the Institute of Wood Science, 8(3): 129-133. SOLSYMBOL 193 \f "Courier New CE"R, R.; MELCER, I., 1992: Structural and chemical alterations of lignin in the process of oak wood hydrothermal treatment. DrevSYMBOL 225 \f "Courier New CE"rsky vSYMBOL 253 \f "Courier New CE"skum, 133:11-22. STAMM, A.J., 1964: Wood and cellulose science. Ronald Press, New York, 549str. 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Journal 19 (2): 37-43. TIMELL, T.E., 1986: Compression wood in gymnosperms I. Springer-Verlag, Berlin TODOROVSKI, S., 1960: Brzina na osruvanjeto kaj gorunot (Quercus sessiliflora, Salisb.) i blagunot (Quercus conferta, Kit.). Godien zbornik na Zemjodelsko-umarski fakultet, Univerzitet-Skopje, Kniga XIII, 1959/60: 167-177. TORELLI, N., 1974: Bioloki vidiki ojedritve s poudarkom na fakultativno obarvani jedrovini (rdeem srcu) pri bukvi (Fagus silvatica L.). Gozdarski vestnik, 32 (7-8): 253-281. TORELLI, N.; UFAR, K.; ROBI, D., 1986: Some wood anatomical physiological and silvicultural aspects of silver fir dieback in Slovenia (NW Yugoslavia). IAWA Bull. n.s., 7(4): 343-350. TORELLI, N., 1997: Osobna predavanja. TRENDELENBURG, R.; MAYER-WEGELIN, H., 1955: Das holz als rohstoff. MSYMBOL 252 \f "Courier New CE"nchen: Hanser Verlag. URQUHART, A.R.; WILLIAMS, A.M., 1924. J. Textile Inst. (15):559-572; 1929.(20):125-132 (iz KOLLMANNA i COTEA 1968) WAGENFUHR, R.; SCHEIBER, CHR., 1974: Holtzatlas, VEB Fachbuchverlag, Leipzig WANGAARD, F.F.; GRANADOS, L.A., 1967: The effect of extractives on water-vapour sorption by wood. Wood Sci. Technol. 1: 253-277. WARDROP, A.B., 1957: The phase of lignification in differentiation of wood fibers. Tappi 40:225-243 u Tsoumis 1991. WARDROP, A.B., 1964: The structure and formation of the cell wall in xylem. u: "The formation of wood in forest trees" (M.H.Zimmermann, ed.), Academic Press, N.Y. WIEDENBECK, J.K.; HOFFMAN, K.; PERALTA, P.; SKAAR, C., 1990: Air permeability, shrinkage and moisture sorption of lodgepole pine stemwood. Wood and fiber Science. 22(3):229-245. WILCOX, W.W., 1968: Some physical and mechanical properties of wetwood in white fir. For. Prod. Journ. 18(12): 27-31. ZIEGLER, H., 1968: Biologische aspekte der kernholzbildung. Holz als Roh-und Werkstoff, 26(2), 61-68. ZIMMERMANN, M.H. 1983: Xylem structure and the ascent of sap. Berlin, Springer-Verlag PAGEVII Trajkovi, J., Utjecaj temperature na sorpcijska svojstva bjeljike i sri jelovine (higroskopnost, sorpcija i vlaga ravnotee u svjetlu osravanja) dokt. dis., umarkski fakultet, Drvnotehnoloki odsjek, Zagreb 1997 PAGE1 Trajkovi, J., Utjecaj temperature na sorpcijska svojstva bjeljike i sri jelovine (higroskopnost, sorpcija i vlaga ravnotee u svjetlu osravanja) dokt. dis., umarkski fakultet, Drvnotehnoloki odsjek, Zagreb 1997 PAGE79 Trajkovi, J., Utjecaj temperature na sorpcijska svojstva bjeljike i sri jelovine (higroskopnost, sorpcija i vlaga ravnotee u svjetlu osravanja) dokt. dis., umarkski fakultet, Drvnotehnoloki odsjek, Zagreb 1997 PAGE65 &27S.A%:7S.A" 7SA.7 7S.AΞ:'pv !  >>???@@@AAABBBCCCDDDEEEFFFGGGHHHIIIJJJKKKLLLMMMNNNOOOPPPQQQRRRSSSTTTUUUVVVWWWXXXYYYZZZ[[[\\\]]]^^^___```aaabbbcccdddeeefffggghhhiiijjjkkklllmmmnnnooopppqqqrrrssstttuuuvvvwwwxxxyyyzzz{{{|||}}}~~~Ϻ~|njvwjfh`D,(4>Hf²~tf[I3  EjƺkP="     1KqԫwW0 0e}տc?+\t͒^4  '/Ef̠|9 (0;EaozǵsH   "&)-/,8@ELIPadmrŪ~WB(" $75Vxƌ@& "TgV@E8! $)" !",Mkt˓H       "+%$%   &   .   $.4/$  8aؠK   !    #% !$+0+!   0Tצc$  $*4&"     " ##G8( :iz5,DG>(AC. !               5EJfR>0#  8uϹz4   /B:*-GUE##  .&    #+$"0%0>9   Cl7 !&($$7J=   7XhT-!"  3;%      )?54*' %    'RԥL -=6%%/0I:1%2/.6*,  %Uդ[ ).;>1-/%:155 #1;2 (          "!'$3+F;'61!',QN78.3<84%!#   =ta             !" ) ?: !'H:$&%2KHB3 ./,=SK8.4- ! 5;!! !. *F[X59KVK{bK2'9GF>0#  "!/@C=YN1 &     yU    4=/ 9PF.      55!+D3 * +?+ - ?K<$"C<'0=bq_cn{WZnqO/.)NzwiW@0$9'""&*=C=FSD#/0#     Πd' ! %1( *:?7#!-AB=4.*)$       #)!0HI1&%/+'*7AD. 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