Handbook of Thermoplastics Polyvinyl Butyral

Home , Laminated glass, Polyvinyl alcohol, Polyvinyl butyral

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Handbook of Thermoplastics

Olagoke Olabisi, Kolapo Adewale

Polyvinyl Butyral

Publication details https://www.routledgehandbooks.com/doi/10.1201/b19190-4 Christian Carrot, Amine Bendaoud, Caroline Pillon Published online on: 22 Dec 2015

How to cite :- Christian Carrot, Amine Bendaoud, Caroline Pillon. 22 Dec 2015, Polyvinyl Butyral from: Handbook of Thermoplastics CRC Press Accessed on: 28 Sep 2021 https://www.routledgehandbooks.com/doi/10.1201/b19190-4

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3.6.3 3.7.1 3.8.4 3.8.3 3.8.1 Applications Blends Composites and Applications and Additive on Effect Properties 3.5.3 3.6.1 3.6.4 3.7.2 3.8.2 3.6.2 3.4.4 3.5.1 3.3.8 3.5.2 3.4.6 3.4.1 3.4.7 3.3.5 3.3.3 Processing TechnologiesProcessing 3.4.3 Properties Polymer Engineering 3.3.7 3.2.1 3.4.5 3.4.2 3.3.4 3.3.6 3.3.2 3.2.2 3.3.1 Structural and Phase Characteristics Phase and Structural Polymer Formation DevelopmentHistorical Commercialization and 3.1.1 3.1.2 3

...... Recycling of PVB Applications Miscellaneous PVModule Encapsulation Application in Safety Glasses Composites Nanocomposites and Blends Retardants Flame Stabilizers UV Light and Antioxidants Plasticizers of Films Extrusion Viscoelastic and Rheological Properties Viscoelastic Rheological and for Processing Properties Thermal Thermo-Oxidation Photoaging and Photodegradation Properties Mechanical Properties Electrical Adhesion Properties Properties...... Surface Density Temperature Conditions Nitrogen) (High in Degradation Thermal Solvents, Weight Molecular and Solution Characterization Properties, Glass Transition Temperature Dosing of Acetate 1 13 Spectroscopy UV Spectroscopy IR Chemistry Postpolymerization Polymerization Data Economic History H NMR Spectroscopy H NMR C NMR Spectroscopy C NMR Christian Carrot, Amine Bendaoud, Caroline and Pillon Butyral Polyvinyl ...... 100 100 100 100 100 120 126 128 104 104 106 106 106 106 122 122 109 130 129 103 112 115 115 115 110 116 116 116 118 118 118 118 114 117 111 90 90 90 96 89 91 91 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 grades meeting the requirements of the solar module industry. solar of the requirements the meeting grades renewed has development automotive the industries the in building crisis and toward effort selected without flexibility additives and for permeability market its properties [5].the superior then, Since of because 1980s, ethylene-vinylthe letting area, (EVA) this in acetate material leading the become of PVBs have in PV market manufacturers the ignored the particular, In of markets. different needs emerging the meet PV) PVB, PVB acoustic, PVB, structural solar PVBs (PVB Specialty-grade stronglyfollowing improved, especially innovations. processing technological performances cal and compositionadjustedphysi been chemical has their because generation first of those to the no longer today are PVBs used comparable application, the though leading the remain products Nevertheless, monomeric of units. the laminated chemistry the to is related capability, turn which in bonding to related owing its to adhesion properties material coating and applications abinder as tive (from 1960), (from building 1980), found has Also,PVB other PV (from industries. and 2000) or without with autoclave)processes productivity of and automo of growth requirements the and (degassing process vacuum of and lamination or vacuum calendering types different meet to glass atlower ofrange temperatures cost. over toughness and awide characteristics cold polymers owingvinyl temperature its to better acetal butyraldehyde from (BA) 1930s, early the prepared PVB was foundother during to superior be to begun already polymers had vinyl of various acetal for automobiles. commercialization the Though glass safety laminated in cellulose replacing nitrate the polymer in wasthermoplastic successful 1935 in Corporation company [4].Carbon Unionof and by chemical PVB Carbide the new The patenting 1930s the to the 1940s others among lead and by during ofefforts anumber companies Ref. [1] for acomplete story), [2,3], subsequent of development large patenting its acetalization and balsam). (Canada resin available anatural with glass to bonded be to material (named Pyralin cellulosewas the nitrate was glass later, set up 30 1935, years but until of laminated facture only interlayer the used be to million. The demand for this product was estimated to increase at an average of atan rate 6%, increase to growth productwas forestimated demand this The million. of size about US$2200 consumption amarket was tons, with resin 270,000 global PVB the 2008, In Europe. is relatively in glazing Europe;its application construction in only 60% in more important but UnitedStates the which windshields, isin about 90% car is use in [7]. Its main materials other glues, 7% dyes, paints, wasin used and remaining the and 4%glass, PV solar materials, wasin used was glass discovered Triplex given and name the laminated The didbreak. flask not the star-crazed that and reagentobserved floorof on cellulosethe nitrate over laboratory. aFrench knocked his scientist, in Benedictus, He flask accidentally aglass Edouard result clumsiness wasof of the the and twentieth of century the layer beginning back the to dates asynthetic with of by discoveryglass for toughening of lamination glass. the demand The safety its and industry development driven by car The the of primarily (PVB) polyvinyl been has butyral 3.1.1 3.1 90 20% (see20% former Hüls plant at Troisdorf the Japan remaining and in control the such Sekisui as companies Solutia that controls 50% world ofestimated the supply of PVB, DuPont controls 30%, smaller and figures. It is capacity reluctant reveal to Solutia both producers, their DuPont, and two main are of worldwide producer PVB Saflex. There main is Solutia, former Monsanto, trademark the with world tons. The over total be to of capacity is notThe but PVB published, it 200,000 is estimated 3.1.2 Since then, the leading manufacturers of PVB have changed their offer of PVB for laminated of have PVB offer of for their changed PVB manufacturers laminated leading the Since then, discovery of poly(vinylThe alcohol) 1924 in (see (PVA) Herrmann by and Haehnel Germany in In 2011,In 89% automotive of for safety and was production PVB used of the construction industry

HISTORICAL DEVELOPMENT AND COMMERCIALIZATION AND DEVELOPMENT HISTORICAL H E Table conomic istory 3.1 ) [6]. D ata ). It was the only transparent, clear, sufficiently). and strong It only wastransparent, the by Benedictus. The process of manu process by The Benedictus. Handbook of Thermoplastics Handbook - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 reaction, one moleculereaction, of aldehyde two with molecules reacts of alcohol (Scheme 3.2). conditions under of acid catalysis. Finally, acetal form to net is used yield ring, the in astable acetal alcohol to another with react further hemiacetals unstable and aldehydean a hemiacetal, produces aldehydes carboxylic alcohols, of nucleophilicalcohol addition of group where the to and the an well-known the Second, between reaction branches. conditions also of oning the polymerization, depend and, vinylmonomersof 1,2-glycol configuration acetate head-to-head come from that units 3.1). tate) of(alcoholysis) by transesterification means catalysisand base with methanol (Scheme usually for production of PVA the PVB. First, material poly(vinyl from is starting obtained tion, is the ace Poly(vinyl by acetate), vinyl suspension from acetate or solution which is polymerized polymeriza 3.2.1 3.2 candidate. second by the EVA, being dominated material athermoplastic as PVB with are prolong to of life PV sealants is panel modules. ameans cell At the the present, sealing and by up years, 20 long life,to generally service PV is characterized panel cell The material. a sealing noise reduction. better for and safe use to glass regulation buildings residential such as trade, building application the in membrane PVB factorsAt promotethe many present, to with 89,000tons,amounted US$614 consumption of films PVB revenue. in sales industry million globalthe construction 2009,In office in buildings. used mainly being glass, safety in embedded relatively of majority not are movable safe the enough. used and at present, fragile materials glass movable side windowsits the in use windows because rear and side and window must hard, very be in of size US$818 is amarket apotential represented There rate. growth a6.5% with annual million films PVB [7], automobile statistics to 2009, According the in industry strict. very are standards used for automotive safety mainly is glass safety industry windshields since where of films PVB customer largest ultimate automotive is the The occupy share. 96%Kuraray market industry of the a2015 410,000 to to amount leading will consumption that tons. and Solutia, DuPont, Sekisui, Polyvinyl Butyral Hydrolysis of poly(vinyl acetate) PVA produces 1,3-glycol also predominantly with and units PV modules as the in is used membrane PVB since is increasing PV of market the demand The interlayer an as material of largest user films second PVB is the industry construction The

Kuraray DuPont b a Manufacturer PVB Producers 3.1 TABLE Formosa Chemicals&FiberCorp.(FCFC) Hindustan Inks&ResinsLtd(HIRL) Sekisui Solutia OYE FORMATION POLYMER

Formerly heldbyHT Troplast andsoldtoKuraray in2005andalsobyClariantsold2002. Eastman Kodak in2012. formed from the demerger fromMonsanto, in September 1997. Solutiahas been completely bought by Monsanto, withtrademarkSaflex, was attheoriginofPVBforinterlayer filmsinglasspanes.Solutia was P olym a b e rization Trade Name Pioloform Mowital Butacite Trosifol Butvar Silec – – Patent 1937 1938 1958 1953 – – Taiwan Japan Japan India USA USA Base 91 - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 SCHEME 3.1SCHEME H 3 C * O

O Transesterification of poly(vinyl of acetate).Transesterification n+ * H 3 C ·OH H 3 C ·ONa H 3 C O * O CH 3 O – * * O – * +H 3 C O O CH 3 * OH

Handbook of Thermoplastics of Handbook 92 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 R can lead to branched and eventually cross-linked polymer. The reaction can be used for the making for making used polymer. be the can reaction eventually cross-linked and The branched to lead can side reaction This formed. also hydroxyl are lecular acetals groups; alesser to extent, intermolecular acetalization reaction of PVAs assuming no vinyl acetate unit. The amount of isolated and unreacted of reaction PVAs unreacted of isolated and amount The acetalization unit. no vinyl acetate assuming adjacent hydroxyl of the PVA limit on the upper groups [9] theoretical the Flory calculated chain, vinylof vinyl alcohol (VA), butyral, (Scheme vinyl and acetate 3.7). PVAto mol%). 2.5 less than terpolymer (generally of a the character producthas final Therefore, the polyvinyl which convertedis acetate during transesterification upstream the from polymer chain the ofpercentage hydroxyl Moreover, groups. always groups acetyl of in percentage the asmall remain given Ref. in [8]. for (Scheme group are anew occur one functional can 3.6). mechanisms original of the Detailed BA with or evenreact (acetal 1,3-dioxane form complete to rings), rings almost exchange partial and yields acatalyst, as hydroxyl PVB. acting acid, The of of groups PVA mineral amounts of small 3.3 3.4) (Scheme reactions and alesser to 3.5). extent, intermolecular and, in (Schemes reactions intramolecular in units various on the proceeds polymerof and any vinyl acetal SCHEME 3.4 SCHEME * 3.3 SCHEME * 3.2 SCHEME SCHEME 3.5 SCHEME * * Polyvinyl Butyral Aldeh From statistical reasons, mainly because the cyclization reaction requires the presence of presence two the cyclization the requires reaction because mainly reasons, From statistical hydroxylSince not all PVA of groups the aldehyde, with acertain react invariably PVB contains PVA aqueous of reaction an the case, solution (BA) aparticular As presence butanal with the in PVA six-membered form to adjacent, between intramo rings aldehyde an with primarily reacts OH yde O +R 1O OH

OH Intramolecular acetalization of the 1,2-glycol of the group. acetalization Intramolecular Conversion aldehyde acetal. to from Intramolecular acetalization of the 1,3-glycol of the group. acetalization Intramolecular Intermolecular acetalization of the 1,3-glycol of the group. acetalization Intermolecular OH OH H OH OH H + *+ * * * + Hemiacetal R + OR1 R H R R OH O H O H H O + R1 –H –H H H + –H 2 OH O + 2 H O + 2 O H * * + ** ** R Ac R OO OO OR1 H etal R O O R H OR1 H +H 93 2 O - * * Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 provides distinct properties to the final polymer. The properties are determined mainly by three three by mainly determined are polymer. properties The final the to properties provides distinct balance conditions,this reaction and on the depends hydroxylresidual rings acetal and groups SCHEME 3.6 SCHEME * 94 to use PVBs use VAto with contents of 9% approximately to 30% by weight ( 82 mol%. Consequently, PVBs always atleast 7% contain by weight VA residual It is standard units. about to products levels commercial higher in limits of acetalization acetalization intermolecular [12]. calculations statistical in account into taken be However, can and of acetalization practice, in levels higher to lead theoretically can interchange was left and Reversibility open. of acetalization irreversible wasization question an but reaction, the reversibility of the rings of of formation acetal acetal that assumed initially Flory Indeed, significantly value notexceeded. been has predicted the above 86.5% of of assumption acetalization irreversibility,achieving degrees the keeping while but values [10]. predicted the exceeding [11] Chanda and Raghavendrachar suggested apossibility of of acetalization adegree with polyvinyl have PVB. synthesize to in Attempts acetals made been VA unreacted an to content 12.25 8.84 wt% between corresponds and this unit, noing vinyl acetate 1,3-glycol PVA BA, with is irreversible. always containing For acetalization acetalization if assum hydroxyl should 0.184 be units mol% for 1,3- 1,2-glycol and PVA containing 0.135 and mol% for pure 3.7 SCHEME HO OH OH OH Since the residual acetate content is keptlow as acetate residual Since possible the as mol%), (0–2.5 between balance the Sekisui Kuraray Kuraray DuPont auatrrTaeNm ACnet(t)VcCnet(t)Reference VAc Content (wt%) VA Content(wt%) Trade Name Solutia Manufacturer TABLE Typical for PVB Contents Monomer

X Acetalization of PVA of BA. case Acetalization the in Terpolymer structure of PVB. Terpolymer structure 3.2 Y O CH 3 Pioloform Z Mowital Butacite O * Butvar S-Lec * + OO CH H 3 3 C 14–18 11–27 11–20 X O OH H Y O –H H CH + 2 O 3 Z O * 0–2.5 0–2.5 0–2 Handbook of Thermoplastics Handbook * Table 3.2 CH 3 OO ). X [14] [14] [13] OH Y O CH 3 Z O * - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Polyvinyl Butyral followingthe equation: composition VA in ( molar the acetate, no remaining is imperative. Assuming components laminate of the the between a good bond adhesionsince glass, to and hydroxyl strength or unreacted provide required groups the atabout 75% is stopped tion of acetalization conversion hydroxyl of the residual the so that groups weight molecular and polymer. of the polarity reac the for PVB For the glass, the safety determine aldehydes, used the they as and of polymerization, degree the offactors: acetalization, degree the SCHEME 3.9 SCHEME 3.8 SCHEME sulfoxidedimethyl (1.4 ×10 (4:1 of DMF/benzene mol% amixture in 90–95 v/v) of concentration ethyl using nitrate acatalytic of PVA,[20] acetalizations various that out including until conversion carried PVB, to could be geneously anon-aqueous solvent nonpolar in when hydrogen least. It was is the reported bonding of PVATheoretically, 100% out acetalization homo should possible be is carried reaction the if is not nonsoluble long. very are reactants of water, the in time acetals contact these the because PVA by action of the aldehydes prepared generally on PVA are However, medium. aqueous an in long ofalso [19] PVB branches described. been has [17].of used ionomer been has groups of polydimethylsiloxane, Grafting polyoxyethylene [18], and conventional the in going way. polymerization then on the 5mol% 3and Ionomeric containing PVB of salt by sodium using the synthesized [15,16], (Schemes 3.8 slightly 3.9). structures the to and different leading be Ionomeric can PVB butyralization of poly(vinylbutyralization BA and of acetate)reaction methanol the with via conducted was also asolvent as (NMP) 2-pyrrolidone for PVA [21]. PVB and methanolysis and simultaneous The High acetalization reaction can be conducted in homogeneous of in conducted be solution can acetals reaction The processes. acetalization High [14] ethanal and butanal of by use both the or furfural of were obtained PVB also grades Special

Poly(vinyl butyral-co-furfural). Poly(vinyl butyral-co-ethanal). m in mol% in VA) weight the of from VA, fraction is deduced * * −3 OO OO CH CH mol/mol PVA); using claimed was also 93% acetalization 3 3 m = 100 X X o 44 -benzaldehyde sulfonic acid in a preliminary step, and -benzaldehyde apreliminary sulfonic acid in OH OH () 100 Y Y −+ OO OO 142 ww CH CH w 3 3 ZW ZW () 142 O O CH 3

O O O * * w in wt% VA, wt% in by N -methyl- (3.1) 95 - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 More detailed schemes of the polymerization arrangements, especially concerning the solvent the concerning pro especially arrangements, schemes polymerization of the More detailed hereafter. today, described commercially are used they and are two variants with basic processes or concurrently. either conducted only sequentially be practice, Hydrolysis can In acetalization and found Ref. be subject in on on the synthesis can [18,27,28]. papers [26] various in details and Other Other cross-linking agents are cited next. cited agents are cross-linking Other promote alow to of cross-linking. amount acetalization the during hyde added be or can trialdehyde improve that urea solubilityin or thiocyanate water. ammonium emulsifiers avoided be shows which can levels by higher acetalization acetalization, aqueous of intermolecular the in resin completion Precipitated reaction. of after the acid. Acidity is neutralized amineral and aldehyde of solution reaction aqueous the the an with of during PVAtated acid acetic containing lowvery levels acetalization. of gel intermolecular from [29]. stability improve to acid catalyst and By-products thermal resin recovered. be Resin has can remove to hydroxide sodium with the hydroxide, necessary or potassium stages are washing and Neutralization, acid of catalysis occurs. the water, into neutralization is precipitated aqueous and PVA PVB reaction, Upon completion acetalization of mixture. the dissolves reaction the in PVB as of solvent the in slurry the process, proceeds reaction acetalization BA acid the catalyst. As the and with heated and ethanol, with slurried being after operation, PVA a separate in acetalized is then by ethyl centrifugation. and acetate ethanol remaining from separated be thereforecipitates can and acid catalystproduce to mineral and a ethanol pre that with PVA transesterification by saponified Poly(vinyl used. be tate) hydrolysis cannot content, simultaneous acetalization acetate) and is first Ref. in [3]. described are ing for engineer process, aqueous chemical the hydrolysis and usingcess sequential acetalization and known are five[23–25]: differentprocesses [22]. reactants of the vapor 70°C pressure atthe from 90°C to batch conditions under polyvinyl attemperatures acetate 96 polyisocyanate enable curing at room temperature with acid with catalysts. temperature atroom polyisocyanate enable curing aldehyde (Scheme 3.14), formaldehyde [30]. and used be well hydrate as can as melamine Urea and Phenolic (Scheme 3.10), (Scheme melamine 3.11), epoxy (Scheme 3.12), (Scheme isocyanate 3.13), of number available. OH on groups the depends capacity cross-linking The resistances. thermal owing improve to order species in OH to various groups with solvent, cross-linked and chemical, is soluble that of solvents, number alarge organic in material is athermoplastic PVB but be it can 3.2.2 The solution process is carried out in an organic solvent. organic an out in To solution poly(vinyl undesirable The the is carried process limit ace found Ref. be in of can PVB polymerization [3]. and ingredients of list on the patents A detailed To average the weight increase molecular polydispersity, and of dialde quantities various small water, out in where PVA is carried process aqueous The dissolves easily. is precipi acetal The Finally, from the chemical engineering point of point view, engineering Finally, chemical of the poly(vinyl for from preparation the acetal), 2. 4. 3. 5. 1.

strong mineral acid and acetalized at the same time. same atthe acetalized acid and strong mineral poly(vinyl The reaction. acetate) is dissolved asuitable in solvent is hydrolyzed and by a poly(vinyl of conversion Direct acetate) poly(vinyl to acetal) Heterogeneous reaction water, with continuously is mix added which prevent to can acetal, precipitation. Homogeneous reaction out heterogeneouslyand completedis homogeneously. reaction The starts product. final the Dissolution precipitates. changes reaction aheterogeneous to acetal phase when reaction the Precipitation

P ost p olym . PVA powder asuitable in is nonsolvent suspended dissolves that aldehyde the and . An aqueous solution aqueous . An of PVA homogeneous aldehyde the the with until reacts e rization . The reaction starts in awater solution in of PVA. starts reaction . The Asolvent for the . PVA aldehyde. the with reacts or fiber film form in

C he mistry . This is also ahomogeneous is also . This Handbook of Thermoplastics Handbook ------Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 SCHEME 3.10SCHEME * * OH

+ Reaction of PVB with phenolic compounds. phenolic with of PVB Reaction HO CH OH 3 R OH CH 3 OH + HO * * –H H + 2 O * * O OH CH 3 R OH CH 3 O

* *

Polyvinyl Butyral Polyvinyl 97 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 SCHEME 3.11SCHEME * * OH +

HO Reaction of PVB with melamine. with of PVB Reaction N H NN N N H R N H NN N NO H H + HO * * –H H 2 + O * * O N H NN N N H R N H NN N N H O

* *

Handbook of Thermoplastics of Handbook 98 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 SCHEME 3.12SCHEME SCHEME 3.14SCHEME 3.13SCHEME Polyvinyl Butyral * * * * * * OH OH OH OH

+ + + Reaction of PVB with epoxy compounds. with of PVB Reaction Reaction of PVB with isocyanates. with of PVB Reaction Reaction of PVB with aldehydes. with of PVB Reaction OCN H OO OO R R R NC O H + + + HO HO HO HO * * * * * * NR H –H

3 + H 2 + O * * * * OO ** * OO OO N H O OO OH R R R N H OH O * * * * * 99 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 (in the region 1050(in the between 1150 and cm TMS as the internal standard. The The standard. internal the as TMS Administration 21 CFR. Administration nontoxic Mowital suitable are and US to Drug and for and Food according food packaging dioxide. carbon Butavar produce combustion,system causecoughing.Underwill PVB and air eyes, respiratory and throat, themselvesirritate dust, which protect to can the from need still is acolorless for process used PVB product. the odorless and powder.is not ahazardous Users develop to exerted been has effort [31–33]. reliable toolsanalytical for its characterization PVB morphology of and blends. behavior, miscibility Therefore, affects much and cross-linking influences resin, example, of improves thermoset it adhesion surfaces, to properties controls the strongly hydroxyl dependent on the are properties and content. For Structure units. meric VA, of composed Finally, vinyl butyral, terpolymer is a random PVB mono vinyl and acetate 3.3 100 Figure 3.4Figure gives example an of 3.3.4 CDCl (DMSO)-d6 in for and low acetalization sulfoxide dimethyl in solvents, solubility various the of in of must PVB obtained PVB be spectra in is reflected degree [36]. acetalization Since structure the PVB the copy determine to is useful of PVB, nature terpolymer the to Due 3.3.3 hydrogen bonding. intermolecular and molecular involved groups cyclic- functional polymer backbone, the intra present electrons in all in C−O−C of oxygen and tion characteristic C=O acetyl ofor OHof groups, due electrons the the to lone pair for forobserved is expected π nto to PVB hydroxyl-containingrelated groups at415 UV shoulder [35]. at390 nm asmall ataround band and band absorption nm absorption The analysis shows of UV–vis PVB. The spectra spectral astrong absorption 3.2Figure UV exhibits the 3.3.2 at3490 cm vibrationing bands PVA, to attributed - showOH peaks with stretch typical spectra (FTIR) infrared transform Fourier ir S 3.3.1 acetalization by following the equation: acetalization Table thein it enables of the quantification extent of of structures, 3.5. addition confirmation to In (CD ture fraction of acetal rings are correlated. are rings of acetal fraction ture - VA stereostruc racemic remaining of the the and [38].peaks of acetalization degree the course, Of PVA of parent diads racemic meso and (Scheme 3.15), responsible also racemic for meso and the of states isomeric rotational due the to are conformations ring acetal carbon, asymmetric with unit (r) racemic the and [21,26,36]. meso (m) and any vinyl stereostructures in as monomeric Indeed, given are in shifts chemical and ofassignments peaks Figure 3.1group. Figure and (CDCl

3 OD) [37]. used was also

STRUCTURAL AND PHASE CHARACTERISTICS PHASE AND STRUCTURAL 3 with tetramethylsilane (TMS) as the internal standard. The The standard. internal the as (TMS) ) is given 3.3 Figure tetramethylsilane with in 1 UV S 13 H NMR S C NMR S pectroscop pectroscop pectroscop pectroscop Table y y give the assignation of the various peaks [21,34].3.3 give peaks assignation various of the the 13 1 C NMR spectrum of (90 PVB mol% spectrum VB)chloroform deuterated in C NMR −1 H NMR spectrum in DMSO-d6 of21–27 with PVB DMSO-d6 in using VB wt% spectrum H NMR y , plus absorptions arising from the presence of acetalic functions functions of presence acetalic the from , plus arising absorptions y 1 H NMR assignments of peaks and chemical shifts are given are shifts chemical and of assignments peaks H NMR 1 H and H and −1 ). The band at1740). band The cm 3 13 for high acetalization rates. Deuterated methanol methanol Deuterated rates. for acetalization high - spectros (NMR) resonance C nuclear magnetic Table the with 3.4 correspondence in −1 appears because of the acetate acetate of the because appears Handbook of Thermoplastics Handbook * electronic transi * electronic 13 C NMR C NMR fi gure gure - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Polyvinyl Butyral Electrochem. Sci., Electrochem. 3.2 FIGURE 3.1FIGURE

FTIR spectrum of PVB with 24–27 wt% VA. wt% 24–27 with of PVB spectrum FTIR UV absorption spectrum of PVB with 18–20 al., et VA. with of wt% PVB E.E. Kalu, (From spectrum absorption UV 7, 5297–5313, permission.) with reproduced and 2012. Adapted ESG. © Copyright

Intensity (u.a.) % Transmittance 100 20 40 60 80 10 20 30 40 50 60 70 80 4000 350 0 0 2850 and3000 3490 Wave (cm Groups of Functional IR Assignation 3.3 TABLE 960 1100 1200 1740 1400 and1280 3500 OH 400 − 1 ) Aliphatic 3000 450 Wa Wa venumb 2500 veleng CH 500 ers th (nm) 2000 (c C=O m 550 CH CH –1 C–O–C (VB) Acetal (VB) C=O (VAc) 1500 ) OH (VA) Alkynes Groups 2 3 , CH

Ester CH C–O– 3 600 2 1000 , CH C C– O 650 500 Int. J. Int. 101 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 102 SCHEME 3.15SCHEME 3.3 FIGURE 102, 5007–5017, Sci Polym JAppl M.al., et Fernandez, 2006.)

13 C NMR spectrum of PVB (90 of mol% PVB VB) CDCl in spectrum C NMR Meso and racemic stereostructures of PVB. stereostructures racemic and Meso Source: 6 5r Assignments of Assignments 7 5m 4r 4m 3 2 1 Number TABLE 4m * 100

4r 3.4 Dhaliwal, A. andHay, J.,Thermochim Acta391,245–255,2002. Fernandez, M.etal.,J Appl Polym Sci 102,5007–5017,2006; Meso-rin 1 3 4 2 C Racemic butyral O–CH–O 06 40 60 80 OO 3 Meso-butyral O–CH–O H Racemic butyral CH 13 7 Vinyl alcohol–CH OO Vinyl alcohol–CH Meso butyral CH s5 gR tutrlUi Chemical Shift(ppm) Structural Unit C NMRPeaks Butyral CH Butyral CH Butyral CH OH m 755 5r 76 663 * ppm 2 2 3 2 * 3 O acemic-ring 3 with TMS as standard. (Adapted from (Adapted from standard. as TMS with 13.7–18.1–18.2 20 105.5–105.6 2 68.0–69.0 72.4–72.5 76.4–78.8 49.3–49.4 41.1–41.6 46.6–46.8 41.1–41.6 21.9–22.0 98.5–98.6 C Handbook of Thermoplastics Handbook 1 3 H 7 O * 0 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Polyvinyl Butyral 40% produces blue. produces 40% content gives ayellow color, gives 15–27% abluish-green 27–40% color, green, produces over and sample changes ontion aPVB its placed color 15% afew in less with than PVB seconds. acetate Ref. to According solu [39], by dosed asimple be Iodine–iodide method. can of acetate quantity the 3.3.5 3.4 FIGURE for better assignment of the peaks. of assignment for the better J-resolved coupled two-dimensional to spectroscopy techniques NMR carbon proton and both use be in Ref. found can 110 to 60 interpretations [37], from those finer which Other ppm methines. to methylene to 15–50 range the ppm correspond in and resonances All rings. of butyral structure The dioxymethine protons 4m and 4r could be utilized to determine the fraction of the stereo of the fraction the determine to utilized 4r could be 4m protons and dioxymethine The

D osing

1 Number of Assignments 3.5 TABLE Source: 5, 7,8 4r 4m 2, 3,6 1 H NMR spectrum of PVB (24–27 wt% VA) wt% (24–27 of PVB standard. as TMS DMSO with in spectrum H NMR

Fernandez, M.etal.,

A 5 c 4r 66 e tat 4m OO 55 Racemic butyral dioxymethineO–CH–O e 1 3 4 Meso-butyral dioxymethineO–CH–O 1 2 Butyral andalcoholmethylene CH 5, 7,8 H NMR Peaks Methine butyral CHandvinyl OH 43 6 O 7 Butyral methyl CH J Appl Polym Sci 8 Structural Unit VB =    3 ppm A A CH CH 102,5007–5017,2006. 3 2 3 2    2 − 2, 3,6 6 2

10 1 Chemical Shift (ppm) 3.6–4.4 1.2–1.8 0.95 4.8 4.6 (3.2) 103 - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 of of by (74 Dhaliwal [36]. K) (18 Butvar PVB is 358 on unplasticized values Higher were K. reported VA) wt% [41] at80°C and mol%) of50 with mol% PVB that 330 K, is nearly mol% is of80 350 with aPVB that whereas K, 104 The useful relations among molecular weight, intrinsic viscosity relations [ weight, molecular useful among The intrinsic s 3.3.7 VA upon the increase content molar ( VA the by varying detail in content [8,21,40], was found to temperature transition glass the and studied effect been vinyl ofable of has The the transition PVB transition. content glass glass on the of PVA that approaching displays and easily observ an [40].is amorphous PVB cases, other all In was found 171°CVA) between be to melting temperature the and crystallizable, are 218°C, and VA only high polymersavery Generally, with is amorphous, PVB 63.3 than wt% content (higher g 3.3.6 102, 5007–5017.) Sci., Polym JAppl M. al., et Turk al., et JChem 3.5 FIGURE leads to a significant departure from groupadditivity. from The T departure asignificant to leads content of the hydroxyl in hydrogen in increase increase bonding, which gives an to groups rise and slightlyand less (2.52 × 10

cosity cosity parameter depends on the hydroxyl on the depends at 25°C. content Kparameter 2.89 being ×10 The = 0.72,a = K For PVB, the Mark–Houwink exponentFor Mark–Houwink PVB, ( the η r are given in the following (in which all constants are solvent- given following are the are in constants (in whichtemperature-dependent): all and ol lass

ve Variation of the glass transition temperature of PVB with the VA content. (Data from Zhou, Z. Z. VA Zhou, the from with of PVB (Data content. temperature transition glass Variation of the H nts T =0.41 K and g/dL, 82, 2934–2946, 2001; Fernandez, 2001;, 21, 2934–2946, Fernandez, 82, Sci., Polym 1997; 229–238, JAppl al., et E. Cascone, ransition , S ol the Huggins and Kramer relation: Kramer and Huggins the u

tion Glass transition temperature (°K) 330 335 340 345 350 355 360 −4 the Kramer relation: Kramer the T mL/g) for 10 VA wt% [42]. Resultsglycol in [43] ether showed values 01 e the Mark–Houwink relation: Mark–Houwink [ the P m ro pe 020304050607 rat pe K =−0.10 for VA. g/dL 22 with wt% PVB refraction and Virial rti Casc Z Fe F u hou etal. igure igure rnandez etal. r es e one etal. , an a VA 3.5 ) has been found to be 0.72 in tetrahydrofuran (THF) found 0.72 (THF) be been to ) has tetrahydrofuran in d content(mol%) M ). Butyral groups have ). groups the effect, Butyral and a plasticizing ln () C ol η r ec =− u η lar C ][] [] sp ηη η W =+ ] =KM 08 ][] [] KC g ηη oflow with PVB VA content (10 e K ig η 09 ], and specific η ], specific and h KC t a Handbook of Thermoplastics Handbook 2

C H 0

h 100 aract 2 −4

mL/g for mL/g VA wt% 20 e rization sp or relative- vis (3.5) (3.3) (3.4) - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 the total solubility parameter of the repeating unit δ unit repeating of the solubility parameter total the [48]. blendconcept and miscibility dispersion, polar,hydrogen and The and contributions bonding [31]. VAand (DMAc) solvent content the 0.5% (LiCl) using with as dimethylacetamide chloride lithium of weight molecular (MWD) for was distribution used determination (NP-GPEC) chromatography polymer elution gradient by Normal-phase low-angle (LALLS). demonstrated lightscattering laser of weight molecular gives accuracy and aggregates averages better as eliminates HFIP Indeed, [46], but hexafluoroisopropanol asolvent as weightmatography used (SEC). molecular be the can of by PVB measure to SEC THF [13,14].250,000 g/mol by size-exclusion weight molecular determined chro be The of can PVB solventeither individual polymer to leads aggregation. that T indices increment d increment indices Polyvinyl Butyral 3.26, 8.87 and MPa other calculation methods (see methods calculation Tableother 3.7 valuesdifferent were found by Hoftyzer–Van using the or groups Krevelen of structural method able The solubility parameters have been given by theoretical analysis using the solubility parameter have given solubility analysis using solubility been the parameter by parameters The theoretical Most of the industrial PVBs haveMost weight industrial of the average weights 40,000– range molecular the in Source: DMAc–0.5% LiCl Acetic acid Acetic acid MIBK/MeOH (9:1vol) MIBK/MeOH (1:1vol) MIBK/MeOH (3:1vol) Methyl isobutyl ketone (MIBK) Methanol (MeOH) Methanol (MeOH) Solvent Data Solvent Polymer 3.6 TABLE Mowital B60H uvrB7,B7 11–13.5 17.5–20 Butvar B-76,B-79 Butvar B-72,B-74 Butvar B76 Mowital B60H Mowital B30H Mowital B30T Name Parameters Solubility TABLE 3.7 uvrB9,B9 18–20 Butvar B-90,B-98 3.6 . For methanol and methyl isobutyl ketone, most mixtures are better solvents better methyl are and for. For isobutyl methanol than PVB ketone, most mixtures

692–699, 1986;Paul, C.andCotts,P., Macromolecules 20,1986–1991,1987. Data fromStriegel, A.M., Polym Int53,1806–1812,2004;Paul, C.andCotts,P., Macromolecules 19, 1/2 n /d , respectively, 7.62, for and VB 6.80, 11.54, 15.41 and MPa c of43 with PVB mol% VA found Refs. be in can [19,44,45] to according VA (wt%) 151. 18.6 11.5–13.5 18–21 18–21 18–21 24–27 (HFIP) is required for VA with PVB is required [47]. 20% (HFIP) contentthan higher Temperature (°C) ) [49–51]. 35 80 25 25 25 25 44 50 25 15.5 20.2 18.6 19.1 17.7 21.2 21.7 δ D D , δ P , δ H 11.2 12.9 , and δhave, and found 7.72, be been to 2.90, δ 6.5 9.5 4.4 7.2 8.7 7.9 P A 2 (mLmol/g 0.00139 0.00104 0.00015 0.00036 0.00079 −0.5 – – 2 10.4 13.3 10.3 12.2 13.0 12.6 14.0 14.6 ) δ H 1/2 for VA. Overall, 0.1120–0.1145 Reference 0.0570 0.1302 0.1173 0.1062 0.1284 0.1015 0.1676 0.1562 dn/dc [50] [49] [49] [51] [49] 105 - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 decomposition temperature can be delayed [29]. be 330°C can air until in decomposition temperature starting of the PVB, and addition of such stability bases hydroxides the as the increases part, ( to 1.100to g/cm content is clearly the important parameter, whereas molecular weight has a secondary effect. weight molecular whereas asecondary has parameter, content is clearly important the Pioloform, (Mowital, PVB solubility Butvar) and the of solvents. commercial various in VA The loss 50%, of and 40% respectively ( at316°C two maximum place with steps in decomposition of takes PVB at382°C and weight and aweight with at 280°C decompose ForVA at480°C. 90% higher loss and 80% between content, of to one percentage stepwhen VA place in the takes PVB starts 80%, PVB and is less unit than Hydroxyl of [8,21]. PVB stability effect have on the groups adramatic decomposition of The 350°C 445°C. and above cyclic formed and Finally, are 445°C compounds cross-linked [52]. step, scission.second 85% the chain In between polymer of is main degraded the and groups of side degradation stepis the second The of350°C butanal. amount formationof with asmall VA the from steps: 315°C between First, water three place in copolymer is eliminated takes and of PVB degradation 3,5-diphenyl, detectable. The also 1,2,4-trioxolane, are 2,4-hexadiene and butanol. such Traces 1-phenyl and as chemicals of other ethanone, 2,5-dihydrofuran, acid, acetic Section 3.4.7. in addressed butanoic acid, BA, are 2-butanal, of products degradation main The be will air in degradation thermal properties, it processing As relates the to at200°C. air under 280°C at decompose to of (ramp and5°C/min) product. nitrogen, Under starts final PVB of the issue for quality is acritical the of sintering process the during ics processing, its elimination for abinder as used ceram being PVB with spheres have by authors.Indeed, many studied been atmo various in temperatures of athigh PVB degradation thermal and thermo-oxidation The t 3.3.8 strong bases. and weak strong acids, and and to weak resistant content. is also PVB NMP, THF, and but solubility VA isthe strongly composition dependent on the especially and -dimethylacetamide, ethyl N,N acetate, acetate, nol, 2-butoxyethanol, cyclohexanone, alcohol, benzyl 1-methoxy-propanol-2, butyl glycol, n 106 OH groups. OH [55,56]) mN/m (24–25 temperatures at room for VA various contents show influence of little very respectively15.0 mN/m, [51]. given Values method tension by Zisman surface the critical of the components of value polar 23.0 dispersion with and of The 260°C. 38 was calculated mN/m and and 240°C between of mN/m dependence −0.6 temperature linear with at240°C mN/m 0.2 [54] tension method drop ofSurface was PVB evaluated by pendant found the 36.4 ± and be to s 3.4.2 1.083 density of from ranges The PVB g/cm 3.4.1 3.4 temperature of 2.52 ×10temperature VA was given for by temperature similar with Wilski contents [53] avalue with with of variation Fi gure gure PVB is solublePVB following the in solvents:- 2-propanol, buta ethanol, acetone, methanol, acid, acetic

POLYMER ENGINEERING PROPERTIES 3.7 D u he e ). rfac nsity rmal 3 at a VA content of 19 (43.1 wt% mol%) [8,13]. specific ofvolume the variation The e P D ro e gra pe rti –6 d es ation cm 3 /g/°C 6.91 below and transition glass the ×10 (H ig Fi h gure gure T e m ). As has already been indicated in the synthesis the in indicated 3.6 been ). already has As pe 3 for aVA with PVB content of 11 (28.5 wt% mol%) rat N,N u r -dimethylformamide, -dimethylformamide, e C on d itions

in Handbook of Thermoplastics Handbook N itrog N,N –6 e -dimethylsulfoxide, n cm ) Table 3 /g/°C above it 3.8 shows -butyl -butyl - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Methyl ethyl Methanol Acetone Butyl acetate Ethyl acetate Diacetone n n Ethanol VA wt% Polymer 10% Various PVB in Indicated Solvents, of Commercial unless Solubility Solution 3.8 TABLE Methyl acetate Butyl cellulose Ethyl cellulose Methyl Tetrahydrofuran ketone alcohol -Butanol -Propanol cellulose 11.5–13.5 Butvar B79 B76 SW S S S S S S S S S S S S S Mowital B30HH 11–14 PS S S S S S S S S S S S S S Mowital B60HH 12–16 PS S S S S S S S S S S S S S Butvar 18–20 B98 B90 SW PS PS PS PS S S S S S S S S S Mowital B20H B16H 18–21 PS PS PS PS S S S S S S S S S S Mowital B30H 18–21 PS PS S S S S S S S S S S S S Mowital B45H 18–21 PS PS PS PS S S S S S S S S S S Mowital B60H 18–21 PS PS PS PS PS S S S S S S S S S Mowital B75H 18–21 S S S S S S S S S S I I I I a 17.5–20 Butvar B74 B72 SW PS S S S S S S S S I I I I a a Mowital BX860 18–21 PS PS PS PS PS PS S S S S S S S S b Mowital B45M 21–24 PS PS PS PS PS PS S S S S S S S S Mowital 24–27 B60T B30T PS S S S S S S S S S I I I I ( Continued Pioloform BL16 14–18 S S S S S S S S S S S S S S c

)

Polyvinyl Butyral Polyvinyl 107 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Note: Source: Dimethyl Acetic acid Xylene Cyclohexanone c b a Toluene Methyl isobutyl Polymer 10% Various PVB in Indicated Solvents, of Commercial unless Solubility Solution TABLE (CONTINUED) 3.8

sulfoxide ketone With ethanal. 14–18 wt%acetate. 5% solution.

I: insoluble;PS:partiallysoluble;S: soluble;SW: swelling.

Technical BulletinN°. 2008084E Kuraray, Polyvinylbutyral ofSuperiorQuality Butvar B79 B76 PS PS S S S S Mowital B30HH S S P S P S . St.Louis,Mo:Solutia,Inc.,2008. Mowital B60HH PS PS S S S S . HattersheimamMain,Germany: Kuraray EuropeGmbH, 2013;Solutia, Butvar B98 B90 PS PS S S S I Mowital B20H B16H PS PS PS S S S Mowital B30H PS PS S S S S Mowital B45H PS PS PS S S S Mowital B60H PS S S S I I Mowital B75H S S S I I I a Butvar B74 B72 Butvar Polyvinyl Butyral Properties andUses. On-line S S S I I I a a Mowital BX860 PS PS S S I I b Mowital B45M PS PS S S I I Mowital B60T B30T S S S I I I Pioloform BL16 PS PS S S S S

Handbook of Thermoplastics of Handbook 108 Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Polyvinyl Butyral 229–238, 1997. © Copyright Tübitak. Adapted and reproduced with permission.) with reproduced and 1997.229–238, Adapted Tübitak. ©Copyright explored. The mono-alkoxy silanes have weak impact on adhesion when compared to untreated explored. have mono-alkoxy untreated to silanes on adhesion The when impact weak compared provenance its Improvements plasticizers. of and PVB of adhesion bycoupling have silane been on the and of acid added organic amount Therefore, sheet. on the adhesion PVB depends tent in the con water adhesionandof regarding provides higher it stability increases acidic modification adhesion the glass, to whereas of PVB decreases modification Alkali water sheets. content PVB in [58], glass ments on interlayers for laminated of activity hydroxyl the on the pH and on the depends hydroxylthe [57]. content work beads on glass on the of adhesion measured measure to According involved hydrogenand silanols are glass with bonding ( bonding glass.to chemical Both for applications technological its being affinity most important the hydroxylThe responsible also substrates, adhesion of many for to are groups PVB its outstanding a 3.4.3 permission.) with &Co.GmbH Reproduced KGaA. Chem Makromol Angew Polyvinylbutyrals. des Wärme FIGURE 3.6 FIGURE 3.7 dhesion

Weight VA Turk al., et ATG lossZ. various in forwith JChem Zhou, PVB (From content. Specific volume of PVB: variation with temperature. (From Wilski, Wilski, (From H.:V. Die spezifische temperature. with volume Specific of PVB: variation P ro

pe 3

Speciﬁc volume (cm /g) Weight (%) 100 120 0.91 0.92 0.93 0.94 0.95 0.96 0.97 0.98 0.99 rti 20 40 60 80 0.9 0 –50 0 0 300 200 100 0 es 30% molVA 82% molVA 50% molVA 05 Te Te mp mp erature (°C erature (° . 1969. 6. 101–108. Wiley-VCH Copyright Verlag 100 0 Figure 3.8Figure C) ) 400 ). 3.9 Figure shows effect of the 500 150 , 21, 109 - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 FIGURE 3.8 FIGURE 110 Typical shown in are dispersion data [30] measurements [64,65] spectroscopy (cf. mechanical current and Section 3.4.5). also larization depo [61–63] measurements bystimulated dielectric detected results thermally been by confirm and relaxation—have αor primary the designated below other the temperature, room and relaxation, ary second βor the designated above PVB, two temperature, room majorIn relaxation processes—one 3.4.4 [60]. group organo functional silane of the penetration by and compatibility adhesion promotion group, suggesting the is controlled that functional amino ofby length the the is controlled adhesion strength the and ofhydroxyl groups aminosilane, amino of and groups PVB polymer [59]. the with moieties the between formation of formacid–base interphases Aminosilanes and surface glass the to bonds of their due stability to adhesion strength enhance alkoxy silanes tri- Di- and surface. mineral the to mono-alkoxy of silane the attachment poor dueglass the to Technol 3.9FIGURE (b) Hydrogen (c) bonding. Covalent bonding. with the deorientation of the aligned dipoles involving aligned of when acetate/hydroxyl the groups deorientation large-scale the the with is associated of βprocess it relaxations.a single a distribution but The has relaxation rather process, polymer.of the activation PVB, relaxation was the for found energy In 63 be to this kJ/mol. It is not it structure and motionis strongly molecular of dependent on the segments occurs, diffusional the dipoles one quasi-stable from position atwhich another. to It is possible temperatures only athigher , 18. 1011–1026.) E l ectrical

Adhesion to glass owing to interactions of hydroxyls with silanol groups. (a) Interacting groups. (a) of groups. hydroxyls groups. silanol interactions with owing to glass Adhesion to Interacting Effect of VA Nguyen,Effect from F.N. (Data Berg, J.C., onadhesion. content and Sci. J. Adhes. P ro OO (a) H pe Work of adhesion (J/m2) 100 150 200 250 300 350 400 450 rti 50 H 0 01 41 82 22 26 24 22 20 18 16 14 12 10 Si O es H Figure Figure (b) HH Si O O 3.10 VA process is attributed to the rotation of rotation the to is attributed αprocess . The (wt%) H Si O O H (c) Handbook of Thermoplastics Handbook Si O

28 Glass PVB - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 10 50 were reported in Ref. in [63].were reported with permission.) with B., glassy plateau atabout G storage of the modulus the from decades [30,63]relaxation process of three decrease ausual with displays usually α transition glass the the around onPVB neat spectroscopy mechanical Dynamic m 3.4.5 given are for dissipationin Butvar PVB and factor temperature atroom stant of dispersion to lower [66]. shifting the temperatures Typicaland butyral) values con of dielectric the substituentgroup of size increasing to with plasticization (formal internal the polyacetals reflect α of the behavior particularly dielectric of and the charges.space Comparisons release of the to trapped attributed been has that temperatures reveal athigh also arelaxation process (TSD) studies depolarization current stimulated Thermally of relaxation times. distribution metrical high-molecular-weight with spectroscopy β samples. The is lower (33 kJ/mol PVB), in to observe itquite difficult conventionalby and becomes dielectric activation relaxation The of energy is frozen. this chain main of the rearrangement conformational Source: 10 10 (Hz) Frequency PVB Resins of Butvar Properties Dielectrical 3.9 TABLE 3.10FIGURE Consistent E values tests, tensile in Polyvinyl Butyral (a) 7 6 3

Can JChem Can Loss factor ε 0.45 0.05 0.15 0.25 0.35 0.1 0.2 0.3 0.4

0 04 080 60 40 20 St. Louis, Mo:Solutia,Inc.,2008. Data fromSolutia,ButvarPolyvinyl Butyral Properties andUses.On-line Technical BulletinN°.2008084E. ec

h , 30, 84–91, 1952, © Canadian Science Publishing or its licensors. Adapted and reproduced reproduced and Adapted its licensors. or Publishing Science , 30, 84–91, 1952, ©Canadian . .0427005 . .06330.0064 3.3 0.0066 3.2 0.0050 2.7 0.0064 3.2 . .3025005 . .20280.0240 0.0230 0.0061 2.8 2.8 3.0 0.0230 0.0220 0.0059 2.7 2.8 3.0 0.0150 0.0130 0.0039 2.5 2.6 2.6 0.0310 0.0270 0.0062 2.7 2.8 3.0 Dielectric properties of PVB (7 wt% VA). (7 of wt% PVB properties Dielectric (a) Funt, (From factor. constant. Loss (b) Dielectric anical ′ε ′ε ′ε ε′ ε″ ε′ ε″ ε′ ε″ ε′ 100 kHz 10 kHz 1 kHz B-72, B-74 Te P mp ro erature (°C = 1 GPa until a rubbery plateau atG arubbery ′ =1GPa until pe rti 100 es ) 2 4 160 140 120 = 2 GPa in the glass state and a rubbery plateau at E arubbery and state glass the ′ =2GPa in B-76, B-79 (b

) Dielectric constant ε 3.5 4.5 5.5 6.5 3 4 5 6 04 08 100 80 60 40 20 relaxation is of asym with Debye type B-90 = 1.2 MPa in shear ( ′ =1.2 shear in MPa 100 kHz 10 kHz 1 kHz Te mp erature (° Table dispersion of various various of dispersion C) 3.9 [13]. 2 140 120 B-98 Fi = 5 MPa, ′ =5MPa, gure gure ε″ 3.11 160 111 ). - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 112 safety glass, by UV stabilizers, may be necessary. The use of PVB in the solar module industry has has module industry solar the of use in may PVB necessary. The be stabilizers, by glass, safety UV in of material capable protection PVB photooxidation additional of the of inducing an PVB, and intensities wavelengths relatively of shorter but still suppressed, are long wavelength lightremains the windshields, for used glass with making of covering photooxidation. sheets PVB the When have of point view the region from shown wavelengths the of short that most detrimental is the studies The conditions widely of moderate been exposure under has addressed. stability chemical coating. issue Therefore, of the or asurface its photo aconsolidant, adhesive, impregnant, an as an of preservation objects museum employedand been has PVB repair 50 years, the For in more than 3.4.6 in summarized 3.11FIGURE Yield stress(MPa) VA content(wt%) Mechanical Properties of Butvar PVB Resins of Butvar Properties Mechanical 3.10 TABLE Breaking strength(MPa) Elongation atyield(%) Elongation atbreak(%) Tensile modulus(GPa) lxrlsrnt tyed(P)D790-59T Flexural strengthatyield(MPa) Impact strengthnotchedIzod Source: Hardness, RockwellE Hardness, RockwellM Typical tensile properties of various commercial unplasticized PVBs at room temperature are are PVBs temperature atroom unplasticized Typical ofcommercial various properties tensile

P St. Louis, Mo:Solutia,Inc.,2008. Data fromSolutia,ButvarPolyvinyl Butyral Properties and Uses. On-line Technical BulletinN°.2008084E. h oto

Shear dynamic properties of PVB (24–27 wt% VA) wt% (24–27 of PVB properties 1rad/s. at dynamic Shear Table de gra 3.10. d 10 ation G´ (Pa) 10 10 10 10 10 –100 10 5 6 7 8 9

an SMSadr uvrB2B4Bta 7–7 Butvar B90–98 Butvar B76–B79 Butvar B72–B74 ASTM Standard d P D638-58T D638-58T D638-58T D638-58T D638-58T D256-56 D785-51 D785-51 –50 h otoaging Te mp erature (° 05 17.5–20 2.3–2.4 C) 47–54 48–55 70–75 83–90 0.587 115 20 8 100 0 Handbook of Thermoplastics Handbook 11.5–13.5 10 10 10 10 1.9–2.0 40–47 32–39 72–79 .7 0.374–0.481 0.477 –2 –1 0 1 110 100 8 5

Tg delta 100–110 110–115 2.1–2.2 18–20 43–50 39–46 76–83 20 8 - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Polyvinyl Butyral the usual sequence of sequence events usual the ( photoaging in visible, under aging near-ultraviolet and photochemical middle, wavelengths, through passes PVB contents [63]. acetate high of out case unusually ofbut the pointed only in course been the also In oxygensbetween [69] followed has VA the acetate byin that remaining the segment.of Influence cycle [68]. acetal the peroxide in intermediates bond is that It weakest C–H was the suggested that of key which photooxidationprocess is the role is autocatalytic, played being by hydro ketones and to givelight or heat, oxygen-centered which subsequently radicals, The yield fragments. molecular split, easily be by action of formationofeventually the either hydroperoxides. the will to latter The of presence oxygen, the which, in most likely representattack, the sites oflead radical structure hydrogens PVA. PVB the present in starting tertiary the present in The carbonyl already groups by wavelengths. these degraded polymer PVB, ishowever, readily Commercial ketonic contains region, near-UV this of the allow lightfrom absorption of should PVB not theoretically structure quite severe in ultraviolet conditions [67]. visible temperatures and atvarious radiation the Although near- to or discolor upon exposure principally cross-link, which may PVB in chain-break, manner involved the mechanisms the of and on understanding renewed interest scientific better the for a Polym Degrad Stab. Degrad Polym al., et 3.12FIGURE [68].ately of length fortime asubstantial Apparently, formationof appreciable the color, which developsexposure ultraviolet, to surprisingly PVB no noticeable yellowness moder when heated hydroperoxides,solid-state have [70]. observed been also However, some had has that amaterial in or by of recombination hydroxyl or chains, chain by homolysis formed the alkoxy radicals and of endspolymer of the segments near byformed scission hydroperoxide-containing in reactions may remove prolonged solid polymer the photooxidation. peroxides after from Volatile peroxides decompositionNevertheless, the to of aldehyde contribute hydroperoxides both acid can and that aldehyde between reaction PVA and a reversal initial of the involved polymer. synthesisof the the in simply as it arises because release of acid. aldehyde The butyric more important is far and (butanal) of release carbonyl, of growth and low-molecular-weightbreaking, by BA predominated fragments chain- of comprises for PVB deterioration the mechanism formationof detailed carbonyl.the The photolysis to more intense content,attributed the group of hydroperoxides; butyral the larger the peroxide content the may in be of decline peroxidefall The concentration. and rise the with ciated subsequent and loss weight in gain closely are discoloration initial occur. and The asso brittleness a notably low level. weight Achange in follows loss when 2–3%, the and reaches trend, same the to declines then and a maximum, through passes of concentration peroxide rises, measured the

Photo-oxidation of PVB (11–14 of PVB Photo-oxidation Feller, L. from R. VA) wt% (Reprinted exposure. UVB under , 92, 920–931. Copyright 2007, with permission from Elsevier.) from 2007,permission 920–931. with Copyright , 92, Parameter –5 10 15 20 0 5 05 0 150 100 0 T ime ofexp F igure igure osur Pe Pe Ye 3.12 llowness index rcent weig roxide content(me e (h) ). At first, during a period induction,of period a ). during At first, ht chang e q/g) 200 113 - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 3.4.7 expected. is when exposed visible to near-ultraviolet and cross-linking wavelengths, temperatures, athigher and chain-break to tends PVB below temperature, transition glass Finally, the temperatures atmoderate chromophores. when in bonds of it the isdisruption exposed occurs bleaching light due to the to whereas yellowing exposures is that photochemical dark, polymer the when is observed is in the many in feature why reason amarked discoloration not of been has PVB substitution. Afurther on apolymer place lower and having the taken of peroxide has concentration in butyral degree decline marked atwhich atapoint the occur to tends process, induced athermally is essentially 114 SCHEME 3.16 SCHEME acids, which into attack easily oxidized are that substances or other acid to materials, attributed decomposition the of from polyene observed be also are of can products PVB residues. Instability aromatic other and but reactions, benzene elimination major these the components from acidtic are above decomposes by 260°C. group side PVB elimination significant. butenal, BA, water,ace and is not up 200°C to sebacate. Nevertheless, loss temperatures processing the of atcommon plasticizer loss plasticizer to by of evaporation case dibutyl the attributed in be can mass change in the 260°C, Below 300–500°C. and regions 200–300°C two between loss distinct in 70% of and 20% occurs plots [36], temperature loss mass against shows from by thermogravimetry, weight that measured samples as PVB cessing [74]. step of commercial stability relative PVB, the plasticized thermal In a favorable pro the viscosity self-heating polymer of and the during the effect it since decreases (Scheme 3.16). cross-linking scission than rather by Plasticization water has plasticizer or by added [52,73], butanal and butanoic butanol, acid, melt reduction of chain the the viscosity and indicates production 100°C of reaches the with temperature when the cyclic moietythe is important butyral of degradation PVB, the standard group. In acetate is the of point degradation initial contents, the [72]. process degradation of acetate case high the In investigated susceptible thermal the to are polymer of being the interlayer characteristic [39]. groups of glasses safety functional the all Almost recycling and [71]aging of the properties mechanical have it since and can optical effect on the an 180°C) of reviewed polymers long-term of and been the view has in stabilization of essentially the (150– processing during conditions encountered such oxidation those mild as of in PVB thermal its to ofDue composition, The plasticizers. sensitive migration is very PVB and degradation the to * O O CH 2 t 3 he O rmo

Degradation pathways during thermo-oxidation of PVB. thermo-oxidation pathways during Degradation * - * O OO xi d ation O 2 * * OO O OH CH 3 H H 3 3 CO CO Or * O OH° H H * O Handbook of Thermoplastics Handbook 2 O O CH 3 O * * O * - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 super time–temperature for and Ferry plateau. Coefficients ofof William-Landel for 1 MPa rubbery the show classical the behavior (>0.1 slight with extension rates behavior shear athigh thickening s is 1.36 K) J(g 18–22 with PVB of capacity heat unplasticized VA The wt% hereafter. are proposed [53] at 20°C nowadays design, afew and widely values forof techniques useful modeling used processing the and useful are packages that software in requested physical, are rheological data and Since thermal, t 3.5.1 3.5 [29].process end synthesis of at the the cium hydroxide,hydroxide, hexamine, like barium bases, and or organic suchasbases, inorganic sodium hydroxide, additionlike or by cal of bases purification neutralized removed are or is why acid materials its That result opening. in these then and 1,3-dioxanethe ring © Copyright 2001 Society of Plastics Engineers. Adapted and reproduced with permission.) with reproduced and Adapted Engineers. of Plastics 2001Society © Copyright 3.13FIGURE modulus (1.3teau MPa) alow and weight molecular entanglementsM between of18 with PVB properties viscoelastic VA wt% linear The [75] show level ahigh pla- of rubbery 3.5.2 the flow properties flowthe properties [17]. activation an ofwith energy 30 kJ/mol [78]. Addition of improve to ionomeric was PVB claimed the modelglycol homogeneous in well Arrhenius very region the (PEG) show viscosity fits the that plateau steady below valueand ( this in shear and extension and shear (extensionalin 0.01 from rate 0.1 to s weight with PVB average weight molecular of 143,000 at15–20°C, both transition glass g/mol and Ref. in [76]. is addressed on a rheological data lamination Other during roughness with correlation enables atextrusion processing. output rate The shark-skin high failure of stress the onset shear high 0.18 is around failure of aconventional identicalthat to which is almost MPa, polyethylene. This of onset stress shark-skin Consequently, range. The awide temperature in it state displays arubbery variation of the heat capacity is 0.577 capacity heat of the K) J(g variation Polyvinyl Butyral

position are also given also position at105°C are ( RCSIG TECHNOLOGIES PROCESSING V he isco rmal

–1 Extensional viscosity of PVB at 105°C. at of PVB viscosity Juang,Y.-J. (From Extensional Sci Eng Polym al., et e , and the thermal conductivity [41] thermal the , and is 0.236 W(m K) lastic P ro

pe an

Elongational viscosity (Pa s) rti d 10 10 10 10 10 10 R es 10 8 3 4 5 6 7

heological –1 for P roc C F 1 igure igure essing = 53 C and P 10 ro 0.01 s 0.1 s 0 –1 3.13 pe . Time (s) –1 rti –1 ). Results on miscible blends polyethylene with es 2 = 256°C). at105°C Extensional measurements –1 10 ), can be found), Ref. be in can [77] avalue with 1 –1 . At the glass transition, the the transition, glass . At the 10 2 e (2670 g/mol). , 41, 275–292. 115 –1 - ) Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 the extruder is necessary to remove mixture impurities such as unmelted solid particles and other other and solid particles such unmelted as impurities remove to mixture is necessary extruder the polymer bythe degassing vacuum. melt of under Filtration the before it flowsdie head theof into zone. Water feeding cause plugging the injection can in from must extracted be premature while delayed controlled; injection yellowness of induce is carefully injection plasticizer can surging, and position melted before the of and addition, plasticizer is partially resin Withcous liquid. PVB, the melts avis into (>200°C) mixture extrusion the of screweffect rotation, the of and temperature extruder. of hopper Under an the by the in gravity is transferred mixture homogenization, the After of additives. amounts appropriate with mixed further silos in and stored additives the cizer, are and complexthe is plasti resin, afilm The into anddelicate. resin of extrusion the process The glasses. safety laminated in utilized films used forcommonly that is PVB is a step extrusion of films The 3.5.3 116 In a limited range of plasticizer amount, the variation of the glass temperature of the mix follows mix of the temperature glass of the variation the of range amount, plasticizer a limited In temperature. transition glass the in decrease the greater content, the plasticizer the in increase the efficiency the plasticizers [83]. of phthalate viscosity reduction. Lower-molecular-weight to comparable gives results, 400) PEG (PEG better weights molecular various with have PEGs forprocess. investigated and been plasticizers as also solvent acommon possibly melt casting or within the extrusionthe in step process in an with amixer, in premixed be can PVB and Plasticizers coatings. in used also are plasticizers polymeric 17–25and of adipates, phosphates, taining VA. wt% mixtures and alkyds sebacid Oil-modified 45 with plasticized wt%, but is aclassical for 30 PVBs wt% with use con amount glass safety PVB) (acoustic 30 wt% (structural and be wt% can PVB). resins PVB lightly cross-linked The 15 emulsions. between aqueous contentbisphenol plasticizer in varies plasticizers The resin Aas biphenyl cells, fuel or its derivatives diglycidyl photoconductors, and electrographic in of ether for cathodes in PEG is acrylics; used whereas aeronautics and in glass foradipates laminated (DHA),pate (DOA), dioctyl adipate hexyl cyclohexyl of nonyl heptyl and or mixtures adipate, [81](3GO or TEGH) or automotive PVB [82]; dibutyl for and sebacate architectural dihexyl adi tetraethylene glycol are plasticizers di- is use given for Ref. their in limits of [80]. the and plasticizers known best phthalate-free The chapter. exhaustivetives; this An in of list class ofis therefore, not addressed plasticizers this [48]. addi purpose of use have these but the have regulations used, Phthalates been restricted polymer [41]. the within for used be this can solubility the parameters with calculation Apriori the by influenced andrichdepleted zones greatly between contentVA with some partitioning is miscibility must compatible plasticizer be soluble The this and and resin, properties. the with rheological and mechanical the concerning especially essential are formulation PVB ofthe the pigments for or inorganic in of colored choice used PVB. plasticizer amount The and stabilizers, additives anti-UV such appropriate antioxidants, with as used commonly are resins PVB The 3.6.1 3.6 (15°C) avoid to must sheet PVB stuck not for be the subsequent blocking because [79]. use polyethylene patterned undercooled or rolled sheet by thin either separated and is rolled sheet PVB of 1.14thicknesses up 3.5 to be Manufactured m. 1.52 can sheet PVB and of width the The mm. 0.76 industry) and (fortectural use). mm applications automotive require Special architectural and 0.38 (for mm atthicknesses moltenof the polymer. archi is mostly sheet PVB manufactured The one to side characteristics surface desired the imparts that surface prepared aspecially with a roll is cast onto exit water-cooled. polymer often the close to film die, of the In the are lips proximity interlayer, PVB of the roughness surface its the and and shape controls die the The contaminants. The glass transition temperature depends on the percentage and type of plasticizer; the higher higher of the plasticizer; type and percentage on the depends temperature transition glass The

ADDITIVE EFFECT ON PROPERTIES AND APPLICATIONS P E lasticiz xtr u sion e rs

F ilms n -heptanoate and triethyleneglycol and -heptanoate di-(2-ethyl hexanoate) Handbook of Thermoplastics Handbook ------Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Polyvinyl Butyral followed [36]. or chromatography spectroscopy by FTIR Macromol Mater Eng Mater Macromol et al., Acta VA) Hay, and A. Dhaliwal, J., from DBS. Thermochim and (Data phosphoric acid, and tris(2,4-di-tert-butylphenyl) phosphite [86]. phosphite tris(2,4-di-tert-butylphenyl) and acid, phosphoric 4-hydroxybenzyl) phosphonate, phenyl of ether 2,2-methylene-bis-(4-methyl-6-tert-butylphenyl) phosphonate, diphenyl-(3,5-di-tert-butyl- dimethyl-(3,5-di-tert-butyl-4-hydroxy-benzyl) taeritrite, propionic ethyleneglycol, acid and of ester 3,5-di-tert-butyl-4-hydroxyphenyl propionic pen acid and of 3,5-di-tert-butyl-4-hydroxyphenylether propionic of ester acid, 3,5-di-tert-butyl-4-hydroxyphenyl [82];sebacate 0.1–0.2 species: classically phenols various methyl among used are of wt% hindered triethylene glycol solubility and tion. DHA of The in antioxidant is lower its solubility dibutyl in than dissolu antioxidant the which decreases interaction, causeastrong polymer–plasticizer plasticizer by of asum of additions its the solubilities Larger predicted plasticizers. polymers and in than better of additives. solubility diffusion of additions the and Uponaplasticizer, small dissolves antioxidant affect they of mobility polymer the chains, increase plasticizers since of stabilizer; amount and type the to it connected and is also of solubilitying. is important, Therefore, limit for as the plasticizers, cloud and insoluble polymer,may separation - become the to phase in giving rise at low temperatures polymer. the to However, polymer melt, the in additives, soluble these which are temperatures athigh polymer. orof use processing the added To during are occurs photostabilizers prevent and it, thermo- oxidation, of whichthe could be PVB properties for optical of reasons ofOne deterioration the the a 3.6.2 n polymer either the byfrom solvents using organic nonsolvents are that polymerof such the as by extraction yellowness. must performed be and not increase can analysis plasticizers of The the adhesion glass to and must lighttransmittance plasticizers not reduce sheet, PVB glass cesses. In pro throughput high in extrusion especially processability or properties improveand film-forming bubbles, undesirable generating sometimes temperature, processing the of modules, affect solar photoconductive the in stress residual control layer glass, adhesion reduce to glass, of laminated [84] case forces of softening the impact absorption in and strain increase polymers, plasticizers VA. wt% of 24 for dibutyl stiffness (DBS) the sebacate containing addition reducing to PVB In in Foxthe law [36]; however, [51]. observed is also of miscibility alimit 3.14 Figure shows results the FIGURE -heptane [36],-heptane fluids, ethylene or supercritical CO [85], supercritical modified or ethylacetate 3.14 ntioxi

Variation of the glass transition temperature with the amount of plasticizer (PVB 22–24 wt% wt% 22–24 (PVB of plasticizer amount the with temperature transition glass Variation of the d ants

–1 , 298, 1259–1268, 2013.) 1000/Tg (K ) 2.9 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3 05 B Dhaliwal andHa endaoud etal. 01 025 20 15 10 We ight fraction(%) y , 391, A. Bendaoud, 245–255, 2002; 30 2 [81], [81], 117 - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 chromophores at least in other polymer systems with acetate groups [87]. groups polymer systems other atleast acetate chromophores in with phenylshown with tendency to incompatibility asignificant had they phosphoniteform because phenolic phenols.the phosphonite, phosphate and produce to which Benzophenone is oxidized has to opposed as exposure [86]. is not consumed or UV may HALS due form that thermal to radicals possibly and 0.1–0.2 wt%) peroxide decompose to aphenolic used (HALS; be phosphonite can (0.2–0.35 wt%). light stabilizer amine Finally, such ahindered combination antioxidants as with by inclusion mitigated the be such can absorber a benzotriazole of as radiation a UV of UV effects efficient The wavelengthefficiencymaterials. highest yields PV specific that thequantum the for the in required is also for encapsulation of the PV transparency modules. High required those desirable for long-term of strong exposure may such particularly PVB be as stabilization UV 3.6.3 118 copolymer (SEBS) as an impact modifier has been used, and the best impact properties are obtained are obtained properties impact best the and copolymer used, (SEBS)been has modifier impact an as additive atoughening as [93]. used be also Combination styrene–ethylene/butylene–styrene with blend the in [92]. can for PVB wt% 40 material obtained be Virgin can super-toughened material For lower VA automotive recycled from windshields, PVB contents, using laminated plasticized of groups nylon-6 favorablyamide were interact to observed VA with phase. amorphous the in blends VA [91]. of wt% total ternary blends the in [90] approximately 40–60 and Methylene and of range nylon-6. 55–70 the and window in is observed Miscibility of wt% VA for PVB in binary blends of PVB, PVA, ternary and overall VA binary both in blend content the demonstrated in as relates the to agent a toughening polyamide forbe 6directly of and PVB polyamide 6. Miscibility to suggested. For agents widely been example, has of been use has compatibilizing reported PVB hydroxyl ends of reactive polyamides or polyesters; the chain of and the groups PVB otherwise, achieved be by the can between reaction Compatibility hydrogenis used. or interchain bonding PVB when plasticized especially polymer matrices semicrystalline toughen to the expected often [89]. However,conventionalin aviscosity ionomeric modifier as was PVB used PVB [17]. is PVB tion, even homologous compositions immiscible blends of be chemical of variation can with PVB composi the in strong to variations of and PVB nature terpolymer due the to particular, In species. molecular-weight polymer polymer other is seldom blends, and PVB between miscibility observed of case most Generally, focus was of the the preferred. on in high- thermoplastics ent as and book pres of the it since aim is not the detail in mentioned of but be blends not addressed will types later solventcommon in a These blends casting by for made film or materials. membranes coating for found polymer be in can PVB virgin Otherwise, injection molding on the machine. or directly melt blended the generally conventional in using the polymers are the extrusion blending technique automotive the from industry. Therefore, particularly glass available recycling the of from laminated become of purity recycled and amounts large of PVB ing, because quite quality good essentially is rapidly increas area polymer. publications of this number and patents in The matrix of the erties prop the modify to component polymer especially blends various in aminor as used been has PVB 3.7.1 3.7 of Mg(OH)position temperature decom the between mismatch of the because difference little made addition phosphorus of red and LOIthe beneficial PVB, effect Magnesiumon effect. of plasticized hydroxidelimited addition a had oxygen oflimiting values. presence hydroxyl index The (LOI) polymer backboneon a the groups had combination low-level with in especially PVB improved significantly that addition phosphorus of red of plasticized retardant flame ahydrated filler-type as (ATH) best trihydrate performed Alumina 3.6.4

b f l BLENDS AND COMPOSITES l lam ig e n h d t e s

an R e d tar UV d ants S tabiliz 2 and the temperature at which the PVB plasticizer vaporizes [88]. vaporizes plasticizer PVB atwhich the temperature the and e rs Handbook of Thermoplastics Handbook - - - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Polyvinylidene fluoride is a crystalline technical polymer whose hydrophobicitytechnical be modulated Polyvinylidene can fluoridecrystalline is a afiller,observed toughening little was composites, as [98]. in mica with and limited, remains izer havereactive for compatibilization blends used other been [40]; effect but compatibil of the the route polypropylene [93]. melt apromising be the can (PP-g-MA) grafted Maleic anhydride and inversion phase and in cross-linking dynamic elastomers after thermoplastic obtaining and phase blends However, show improvement properties. little very of mechanical minor PP the as adding the between hydrophobic and species. PP–PVB overcome to hydrophilic affinity poor the necessary blends in of olefinicpolymers with PVB polypropylene of use suchas compatibilizers the hand, is polypropylene polyamide 6and between acompatibilizer as have PVB use [97]. other failed the On [96]. PA6 to in polyamide 6-6 Attempts in not properties necessary but improves mechanical the [94,95]. 20–35 range wt% for the contents in PVB SEBS Addition (SEBS-g-MA) of amaleated is PMMA is minimized at a certain copolymer composition repulsive due the to between atacertain interaction is minimized PMMA a copolymer to unfavorable which effect the in and PVB between attributed interaction is mainly at22–33 VA. wt% weight compositionmer molecular aminimum with on the and of PMMA This copoly on the depends range melt. miscibility the The in blends obtained certain was in observed low. Polymethyl is not (PMMA) miscible PVB, with but a UCST-type methacrylate behavior phase host of polymer transition the glass when is the especially phases, amorphous the within occurs ers However, materials. transfer amorphous of plasticiz significant latter, it the that may in expected be blends in used with is also PVB behavior temperature, at room owing PVB itsto rubbery ticized for forcasting membranes [119]. ultrafiltration interlayer PVB of the [118],tance poly(ethersulfone) and by blends in obtained used be (PES) can (TPUs) melt-blendedpolyether polyurethanes are thermoplastic for PVB with improvement of resis poly(ethylene-co-vinyl alcohol) (EVOH) UCST LCST behaviors. both generates and Cycloaliphatic PEG [117]. than PVB with compatibility polystyrene (PS), better PS has because Combination with an sifierethoxylated–propoxylated suchas blockcopolymer [114–116] blendswith or ternary by by at 140°C. emul using an occurs tuned be Control morphology of separation can phase the while homogeneous behavior (UCST) at 150°C remain solution 160°C and and critical upper temperature systems show PVB/PEG the an because separation phase induced thermally via have prepared been effect some plasticizing [83]bring or viscosity[78]. modification microporous membranes PVB by melt extrusion [113]. Polyether poly(ethylene-glycol) of the easily melt-blended be can family to blended be PVB with can (TPS) starch such thermoplastic as resources agricultural polymers from field amembrane for in used be pervaporation can [112].and nonpolyesterOther biodegradable VA melt-blending. after of lower is PVB miscible afraction wt% with 20 Cellulose acetate than poly(3-hydroxybutyrate)and [111], wt% 24–36 with PVB in miscibility showing latter partial the have poly(lactic resources investigated, acid) been especially [110] biologicalfrom agricultural and example, coefficient a positive [97,106–109]. temperature polyestersbiodegradable Other coming of presence conductive in fillers properties black (carbon electrical [CB]) interesting to rise as, for giving twisting, of lamellar period of the ashortening content, indicating PVB increasing with decrease spherulites spacings of band PCL the spherulite; banded the in organization lamellar the of regularity the in enhancement include morphological changes also The amarked of centimeters. order therefore, grow to nucleation of on the it the PCL reduces allows density spherulites and the nucleation crystals; the PCL of reduces frequency the few strikingly PVB of percent amorphous addition of a particular, behavior In of PCL. crystallization changes the PVB because also and [104,105] substrate of the degradability change to the ceramics and tapes, green casting, tape in [103]. reported been Biodegradable polyesters such polycaprolactone as (PCL) have tested been have polymerization the during cyclic from by grafting oligomers miscibility inducing and starting incompatibility, provide layer. layering can a protective phase of surface the melt Blending the in or forblending coatings PVB. with [102] improvement In resistance weathering of the of because [100,101].PVB for addressed been Polyesters has polymers that belong also aclass to of crystalline by addition of for PVB applications [99]. membrane of 30 wt% until miscible PVB It with is fully Polyvinyl Butyral Though it is expected to toughen rigid semicrystalline thermoplastic, especially when using plas especially thermoplastic, it semicrystalline toughen to rigid Though is expected 119 ------Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 significant changes in the light transmission. Nanocomposites of PVB and titanium (TiO oxide titanium and transmission. light Nanocomposites the of PVB in changes significant and strength breaking the in increase an with exfoliated structures and of intercalated a mix reached montmorillonite (Cloisite modified cially 30B) [138].wt% 3 of nanoclayuntil nanocomposites All (APS), (OTMS) using (TMCS), commer octyltrimethoxysilane also chlorosilane and and trimethyl such 3-aminopropyltriethoxysilane as ions) melt intercalants the various in with were obtained [137].amounts (cloisite Nanocomposites clays with type montmorillonite of the cat sodium with (PZTs) titanates at85 vol% zirconate lead ceramic by addition of ferroelectric obtained been also [136]. low temperature with and loss variation constant have dielectric dielectric their High tor and change to volume wt% resistivity, dissipation and 60–90 fac range - the constant, in PVB dielectric losses,magnetic coercivity, [135]. saturation and nanopowder in was titanate introduced Barium temperature, reduction of transition and tion glass molding, showing nanoparticles well-distributed ticles - injec in at contents up to 14.5 processed vol% further and spray-dried, were synthesized, humidity sensors. A variety of shown polymer blends sensors. in Avariety are PVB with humidity pyrrolydone [127,128] (PVP) PS [129] sulfonated and for or membrane or polyaniline reported are fibers carbon [125,126].polymers polyvinylsuchas technical blendsFinally,with miscellaneous strong hydrogen with (but of without mesoporous catalyst bonding)and enable preparation the Blends phenolic with (phenol-formaldehyde) resins OH groups the with reaction without chemical moieties [72,123]. forof lower observed PVB been amounts 10 has Miscibility [124]. than wt% of dehydrochlorination PVC the HCl scavenging and by PVB, by interrupting acid or butyral acetic of PVC stabilizer substitution on atoms PVC owing of radical to chlorine athermal chain as act to PVC to comparison in of [51]. plasticizers amount only alimited accept can PVB was PVB reported of plasticizer of since phase, each compatibility the and migration Attention the to must paid be suchtoughening as [93]. mayproperties that additional provide interesting material afiller as used be can cheap recycled material The available plasticized become and market. that on the quality of recycled(PVC) amounts large of of the PVB because excellent have studied thoroughly been (MBS) [122].copolymer of Blends methyl methacrylate–butadiene–styrene polyvinyl with chloride of melt a the in owing by incorporation toughness to compatibilization the and properties optical [121]. by observed AFM been has Recycled blends in of excellent were used with scraps PVB also [120]. chains PVB VA the by spin-coating within obtained morphology of units The films VB and 120 and to enable modulation of the diameter of the fibers fibers of enablethe to and diameter modulation of[134]. the with Nanocomposites Fe nanofibers Forby example, used. electrospinning prepare to at15 was PVB times silica used in wt% conductivity [133]. lower to PVB with thermal the atany amount adhesion glass. to Silica aerogel mixed be for regarding of use strator can silanes the fibers and [132]. matrix between beads melt-blended were Glass with PVB [59], mostlydemonas a adhesion and gooddistribution with material areinforcing by as act PVB with extrusion and mixed fibers wt%)(30–70 Leather resistance. impact and solvent-casting were mechanical generatehigh to combination in with polyamide fibers silica mentioned. these, Among [130,131]have in used been fact, most work ofIn refers the only afew also and nanocomposites, to conventional composites are Section 3.8. in with dealt be also will abinder of use as PVB The addressed. be will binding than applications other functional composites with nanocomposites also,only section the and this In als. involving miner various of mixtures variety agreat in used applications, abinder, been as has PVB sol-gel and for ceramics industry tape green of nanocomposites. Because the its wide in use are most case, composites of matrix developed aPVB the be with this from will Section 3.8. in Apart sandwich PVB, but of on the and this glass based composite material evident an as laminated ered consid be - can glass composites; laminated indeed mostly particulate the address will section This c 3.7.2 addition of TiO the by sol-gelby and brittle casting the were film [139]. prepared in stiff process became PVB Pure The other examples are nanocomposites, though unusually large amounts of filler somewere amounts large unusually though nanocomposites, examples other are The om p osit 2 , with more than atwofold Young’s the more than in , with increase of modulus 2wt% TiO with es

an d N anocom p osit es Handbook of Thermoplastics Handbook Table 3.11. 3 O 4 nanopar 2 2 ------) . Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Polyvinyl Butyral PVB-PA6-PVA Blend PVB with Blends 3.11 TABLE ethanol became drastically lower by mixing a small amount of TiO amount lower asmall drastically by mixing became ethanol of swelling degree in were solubility improved. the abrasion also and The resistances and Thermal cal properties with 5–7 wt% of nanofiller [130] and a glass temperature decrease. Functionalized Functionalized of 5–7 with wt% nanofiller decrease. [130] properties cal temperature andglass a composites Kevlar/PVB showed mechani within nanocomposites high of very these Introduction of solid particles. simple to by mixing colloidal sol comparison melt from in pared compounding dioxide titanium even or with silica both pre when properties more efficient to enhanced generate were 5 wt% ing Sol-gel ethanol-selective permeation. in is generally generation of nanoparticles PVB-PA6 PVB-PA6-SEBS PVB-PA66-SEBS PVB-PA6-PP PVB-PP PVB-PP PVB-PP-g-MA PVB-PP-PP-g-MA-mica PVB-PVDF PVB-PBT PVB-PCL PVB-PCL-CB PVB-PLA PVB-P3HB PVB-cellulose acetate PVB-TPS PVB-PEG PVB-PEG-P(EG-b- PVB-PS-PEG PVB-TPU PVB-PES PVB-PMMA PVB-PMMA-MBS PVB-PVC PVB-phenol PVB-PVP PVB-PANI-SO PG-b EG) formaldehyde 3 PS Humidity sensors Miscibility Miscibility–toughening–tensile Tensile and impactproperties Tensile and impact properties Tensile and impact properties Tensile and impactproperties Tensile and impactproperties Crystallinity andtensileproperties Tensile andimpactproperties Tensile properties,surface Dielectric properties,weathering Degradability Electric properties Tensile properties Miscibility Pervoration membrane Tensile properties Plasticizer, viscositymodifier Permeation, hydrophobicity Membrane, irradiation,tensile Impact properties Ultrafiltration membrane Morphology Optical properties—toughness Toughness, tensileproperties, Carbon fibers Ultrafiltration properties permeation properties, hydrophobicity, resistance properties properties hydrophobicity, surface thermal stabilizer, permeation, Targeted Properties Casting Melt Melt-virgin orrecycled PVB Melt-recycled PVB Melt-recycled PVB Melt-recycled PVB Melt Melt, TPE, dynamic Melt, TPE, Melt Melt Casting Melt, casting Casting Casting Casting Melt Casting Melt Melt Melt Casting Melt Casting Melt-spin coating Melt, recycled PVB Melt orcasting,Recycled or Melt-pyrolysis Spin-coating cross-linking virgin PVB Process 2 , and nanocomposites contain nanocomposites , and [51,72,93,123,124] [100,101,140] [97,106–109] Reference [90,92,93] [114–116] [102,103] [104,105] [120,121] [125,126] [127,128] [94,95] [78,83] [129] [110] [111] [112] [113] [117] [118] [119] [122] [91] [96] [95] [93] [93] [40] [98] 121 - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 taerythritol [141]. PVB–Al(NO taerythritol conductivity.the of yields thermodependence tripen films by casting Doping of silica obtained was by solution obtained 1.5 composite PVB films in until wt% atamounts added mesoporous silica 122 assembly, degassing, autoclaving, [148]. cleaning and possible and shaping, precutting a in After [145–147]. atlow temperature atroom damping frequencies amaximum and deformationbefore a large failure guaranteeing dueto viscoelasticproperties its finally and properties, adhesive its remarkable and due transparency glass, its with to of high compatibility itsbecause high [144], used or gels be resins, als, applications can glazing for is used most PVB laminated commonly materi automotive synthetic and other Though building industries. the in mainly used glass safety and shatter-proof laminated fracture-resistant twobetweencreate to panels glass pressed is film PVB The process. thermoplastic extrusion in a films glass safety produce to plasticizers with combined are weight molecular of ahigh with PVB transparency. Grades retaining control while heat and UV from by of acoustically also, attenuation ofgiven and a glass provide frequencies, protection performance interlayers improve The glazing. of mechanical can the the maintenance the ensuring strength residual a keep impact, will it after risk injury.hand, of the the other On minimizing film the to adhere also byenergy viscoplastic avoids deformation and splinters glass the because projection of fragments resistance).impact layer synthetic The plays impact of the two it roles. dissipates one part hand, On polymer adhesion, elasticity, of (glass those the and glass of the properties the combining material compositeis a glass Therefore,of togetherPVB. one with or more films laminated linked sheets glass or tempered is acombination glass of safety two or more annealed glass. Laminated safety laminated responsible advantagesare excellent safety of and resistance, the special films for transparency. The includelight adhesion glass, to toughness, good good films PVB of the properties outstanding The applications of PVB. is important glass the one most safety of for laminated of films PVB facture manu The elastic, tear-proof films. and transparent, constituent of highly essential lightfast, is an PVB 3.8.1 by hydroxylbonding the groups. covalent hydrogen through and materials on various its to adhesionrelated properties tremendous applications are these All adhesives, enamels, inks. and paintings, coatings, various in a binder as automotive, and for increasingly tecture encapsulation PV of applications, in modules solar and of applications,an number archi enormous glasses suchas forthe safety for checklist fits PVB 3.8 0.1–0.5 wt%. The thermal insulating tests indicate a1–3°C indicate reduction [139]. tests insulating temperature 0.1–0.5 thermal wt%. The is overVisible 72.7%, transmittance is below haze and 2% ATO when the of range content the is in absorbed. fully almost be UV can efficiencyincreased. insulating is ATO the thermal in content, the efficiency increase insulating the of nanocomposites. With ATO/PVB thermal the enhance cantly signifi show addition of can ATO the nanocomposites. UV–Vis–NIR that spectra nanoparticles oxide (ATO) tin Antimony-doped werespectrum. employed nanoparticles ATO/PVB fabricate to UV the with strongly interacting still while visible the in spectrum enable transparency keep to energy-saving in nanoparticles since glass particularly industry glass the in tion of new properties [143]. casting by tape composite prepared sheets conductivity flexibility of composites for cast thermal the [34]; modulates graphite and oriented and toughness inducing properties mechanical and providesgraphene improvements thermal of the coefficient apositive conductivityof obtain to temperature combination PCL with in [97,106–109]; VAs. have investigated is used CB forms. also allotropic using been various materials Carbonaceous [142]ites PVB with and vinyl with nonahydrate acetates nitrate of owing reaction aluminum the to The manufacture of laminated glass is performed through several including steps washing, through is performed glass of laminated manufacture The A wide development is driven by nanocomposites improvement the of genera functional and

s APPLICATIONS af e ty

G lass e s 3 ) 3 sol has been reported as a precursor of alumina fibers in compos in fibers of alumina aprecursor as reported sol been has Handbook of Thermoplastics Handbook ------Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 thickness and therefore is the specific specific thereforeweight is the and kg/m (in thickness of by sum individual the easily calculated be can thickness of 0.38 The thickness mm. individual by 8layers separated each of with of panels PVB glass 4mm ness. For three example, means 444.8 of of sheets 0.38 number thick xxx.y, PVB as ythe mm and panel glass the indicating xxx with to composition referred is often The glass protection. safety explosions, of the enhanced also and and against gunfire, burglary, against and vandalism objects, against of falling people,fall against against level injuries, use: on the and against protection depending of types performance various in interlayer an with combined separated of 0.38 of are glasses PVB. mm Usually, laminated safety of of number PVB. leaves two being of The glasses 2 mm up reach to 18 can thinnest the sheets, hydroxyls resin with competing [3,58]. for surface sites glass bonding on the adhesion by reduce to act wellcan as moisture salts as interlayer Alkanoate the is not penetrated. interlayer.the even reduced, be low,though adhesion is too If will impact an retention glass during propagate through glass the in made cracks because laminate the easily penetrate can a projectile interlayer [58]. controlled the and glass must carefully the bond between be high, adhesion is too If adhesive of the strength the glass, of safety dyes adecorative as element. used be to For laminated allows also addition process ISO EN 12543-4. Manufacturing standard European the to is required excess strength the of impact humidity, of by and PVB creep. Checking adherence, eliminate to sary - neces be possible, can glass. If calendering asecond composition on the depend laminated of the show will bubbles. glass cycle The edge 45°C of the laminated until times pressure; otherwise under adhesion. creates and performed reduction is glass surface the Temperature ontoperfectly fits that of 135–145°C attemperature of and 12sure bars autoclaving the in step, which allows aflow of PVB out- pres ata is carried and PVB adhesion glass the of final exhausting. hotThe rolling than better production ways, both is vacuum method exhausting through the glass of laminated transparency surface the 110°C and 80°C between Comparing surface about glass 30 min. during of laminated conditions hot exhausting atemperature with in below second the and about 25°C 15 min, during two one cold with has periods: exhausting air edges. of The the before glass sealing the laminated the out from exhaust to air used bar) conditions glass. Low (0.5–0.8 are pressure the put around is avacuum into ring bag or avacuum is disposed rubber glass prevent blocking. laminated The of sheet atambient interleavedplastic conditions such an polyethyleneor shipped with as thin to at 3–10°C, refrigerated or shipped Rollsstored usually of interlayeror precut sheet are drum. blanks atabout 85–100°C heated sheet over the shaping stretching atapered byaccomplished differentially is such glass, automobile glass. For as curved curvature windshields, bubbles laminated the in air edge early, causeseal large will which trapping may exhaust stop of the air temperature high too contrary, on while, the seal, low, stage is too cannot glass preheating of the temperature laminated the If composition on the production conditions speed. oven and depending ing temperature with step of autoclaving final the ( during of air [76]. edges avoids clarity the proper get to the and glass Sealing and PVB entrance the between trapped air the eliminate to next Degassing is critical is the and operation furnace. apreheating in before entry performed be can laminate of the composition. desired Trimming on the depending are stacked ofand 18–20°C PVB Glass film. avoidPVB to perature of and glass joining premature aclosed avoid to in chamber assemblyThe is performed dust atarelative of tem 30% and humidity thoroughly. dried and of washed remove to contamination step,traces are washing products glass all FIGURE Polyvinyl Butyral Typically, by other sheets each to of connected is composed two glass sheets safety or more glass 3.15

Wa Process of lamination. Process shin gS ta ck ingP Figure 3.15Figure rehe tn Nip-rolling ating 2 ). This is done by calendering in apreheat in is done by). calendering This ) with a glass density aglass g/cm of) with 2.5 Au to clav e 3 and PVB PVB and 123 - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 124 density of 1g/cm FIGURE in multilayer have 16°C between in grades assemblies. alow These temperature transition glass and used are acoustic PVB changes energy. as heat known vibration into energy that grades Special plastic aviscoelastic with interlayer is used glass laminated attenuation, goodsound obtain to and of To sound. vibration effectively and plasticizer, damping provides the damping PVB also increase for visual improvements. Due to its viscoelastic properties and lowfor improvements. and visual T its to properties Due viscoelastic 3.17) [151,152] holographic or by elements of use diffractive [153]. be used also can Colored films ( addition upon of particles flooring overespecially and time, of colors of fabric, furniture, ties. It enablesrays blocking of 99%UV the of (below the 380 nm) preventing sun of fading the the proper functional interlayer PVB issues,effect asignificant on other the also has tion security to addi In source. external an or to provide shielding from radio-frequency thread the ofcase cutting in alarm layers PVB an the trigger to order between in barely introduced visible be and also can money, (0.08 isdiameter) extremely embassies. in of that and transporting copper thin mm Agrid vehicles [150]. addition glass to fabric in banks, in glazing and counters application from ranges The layered poly(ethylenepositesof afilm are with terephthalate), polycarbonate, or acrylic, or metal such 3663.6 glasses as polymers. com or acombination PVB other with laminated asymmetrical of use event the urban weapons shop requires locations against windows. such high-risk as Security office private residences,blocks, in commercial used be can they requirements, strength breaking Typical mm. 444.12. to × 400 compositions 444.8 on of ‘Depending are 400 opening an make to ax or an of awindow of by destruction to ahammer resistant means are burglary organized against not does heavy use objects. Glasses that developed for simple used be to from burglary protection level. ground to the used compositions also façade glazing These and are partitions, lift partitions, internal balustrades, spandrels, 33.2from banisters, for used balcony 44.6. to are railings, They two layers; with PVB compositions range typical laminated two are panels glass At minimum, fall. the protect place and in must pieces glass remain the building, forof fall, example, atall in windows, shower risk with injuries bus shelters, Foragainst roof glazing. protection screens, and of layer, one PVB doors, it aminimum two uses with for panels in and glass is used the This prevent hold together pieces dispersion. and glass dangerous the will PVB their cracks, glass the awindow. against shocks of falling aperson must glass If safety withstand the aglass, against 3.16 cony, including shop riot explosion display, and burglary, vandalism, against ( protection and In architecture, for protection of, or simple security to protect, people from accidental impact impact accidental people from for of, protect, to protection or simple security architecture, In ) [149]. ) 3.16

Various configurations of laminated glass. laminated of Various configurations 3 . Double- or triple-laminated glasses are used for separation, stairwell, roof, bal forstairwell, used separation, are glasses . Double- or triple-laminated Against weap St nad(31 Againstinjuries(44.4 andard (33.1) Gl as sP ons (a symmetric VB ) Against weap PU )A gainst burglar PC ons (c om Coating Handbook of Thermoplastics Handbook g po y (444.4 especially upon addition of a especially site ) ) Figure Figure F igure igure - - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 motive glazing such as comfort, security, and environmental issuesaddition safety. to in environmental security, and motive Modifying such comfort, as glazing was developed for laminate resistance passenger safety. for nowauto New are required functions 1935 in UnitedStates by the law in 1938. regulated in and introduced 1964, penetration In high a50% inducing reduction of perceived noise [159]. through sounds irritating ( band Hz 1000–3000 the in For example, of use yields acoustic glass PVB the 10 of noise dB reduction laminated for a6mm duced with permission.) with duced 1–11. Techniques l’Ingenieur. de Techniques repro Editions l’Ingenieur. de and © Copyright Paris: Adapted 2013. feuilletés, Techniques l’Ingenieur, de verres In AC41). N4404, pour G., Intercalaires Savineau, (From permission.) with reproduced 2010, and Adapted 777–778, IEEE, IEEE. ©Copyright 3rd International, (INEC), Conference 2010. novelwith UV-shieldingIn Nanoelectronics properties, films nanocomposite ZnO/PVB transparent FIGURE 3.18FIGURE load) wind of is 10 conventional that of atypical less ( 100 to than PVB times 18°C, relaxation modulusat3s(which therefore at20°C the and representative is considered be to 3.17FIGURE Polyvinyl Butyral Looking at the history of automotive glazing, laminated glass with a PVB interlayer a PVB with glass of was automotive first history at the laminated glazing, Looking

Storage modulus and damping of(Saflex conventionalRB11) PVB damping and modulus Storage PVB acoustic (Saflexand UV shielding by ZnO nanocomposites. (From Zeng, X.-F. Zeng, (From of highly nanocomposites. by Fabrication al., et ZnO shielding UV

Storage modulus (Pa) 100 120 10 10 10 10 Transmittance (%) 20 40 60 80 200 0 5 6 7 8 . 002. 004. 0060.0 50.0 40.0 30.0 20.0 10.0 0.0 Figure 3.19Figure 0 0 0 600 500 400 300 ), which is the noise transparency range that lets the most lets the that range ), noise which is the transparency Te Wa mp veleng erature (° th (nm) C) Ac St andard 0.2 wt% Zn 0.2 wt% Zn 1 wt% PV oustic B PV PV 700 O B B O 0 1 2 800

Tg delta F igure igure 3.18 ) [154–158]. 125 - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 2004, 62–65, Yoshioka, 62–65, T. Springer.)2004, ©Copyright Science+Business Media: AutoTechnology Media: Science+Business 126 line Si wafers are encapsulated between two between layers Si encapsulated wafersline are of ( PVB reliably modules using solar crystal Classical practice. in properties of displayplastics these that all (to protection UV high prevent and plastic). of the degradation transparency fewhigh are There contact), film, and obviously backing cell, module components (glass, adhesion other to adapted oxygen to water barrier vapor, and resistance, impact preventiontion, external of corrosion, cell - insula electrical weathering, from protection cell, of protection the such mechanical as features long-termity and important power have generation, encapsulation display cell to materials certain under have GmbH Trosifol with successfully films modules usingbeen Solar PVB Europe trademark. worldwidemanufacturer developto modulesfirst Kuraray in wasfilm use for solar PVB a special The long-term of the to generationsunlight. PV modulesfrom and of durability electricity the to contribute modules.for solar plastic encapsulationmaterials required is Transparent influences for EVA as cells solar copolymers. Reliable external long-term of from cells and protection solar rolenowadays, encapsulation aleading alternative among materials assuming is increasingly PVB driven intensive developments and encapsulation,module for solar toward of use films PVB the level high and of 1980s, lamination Since control technologiesthe experience of in has these the m 3.8.2 pigmentedresin. with by coextrusion interlayerfor onor tinted the automotive surface is printed band windshields. The average weather condition Colorado in [161]. interlayer made An color is also gradient with bands visible in light[142], vehicle the in bytransmittance 1°C temperature amidday in air decreasing 70% and IR and developed UV in been forPVB absorbance also has high windshields very with noise engine to [160]. associated band Hz 100–300 the in control Solar increased is particularly Damping ease. handling and outer layers as resin strength PVB for mechanical normal and mance alow has example, make-up elasticity acoustic perfor three-layer layer PVB for acore as maximum For atambient of for temperature. low because damping elasticity required orhandling softness and strength of interlayer mechanical PVB terms acoustic interlayer in normal the the to is inferior Indeed, resistance. improvedhigh byof mechanical use a multilayer the keeping films, further be interlayer PVB waythe can and is new apractical Noise of functions. adding reduction is targeted 3.19FIGURE going outdoor weathering tests since the beginning of the 1980s. of the To beginning the since tests going module durabil ensure outdoor weathering o du

Noise reduction for various laminated glass. (With kind permission from Springer Springer from permission kind (With glass. laminated for various Noise reduction l e E nca p s

u Transmission loss (dB) 15 20 25 30 35 40 45 lation 64

in 2 5 1 1024 512 256 128 PV A , Functional laminated glazing with advanced PVB technology, PVB 4, advanced with glazing laminated , Functional pp Fr lication equency (Hz) equency Mu Ac St (3+3 mm) Glass F andard igure igure oustic 084096 2048 ltil ay er PV PV PV 3.20 Handbook of Thermoplastics Handbook B B B ) and glass. In thin-film PV thin-film glass. In ) and - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 Ionomer and PVB offer higher protection from environmental exposure for thin-film modules than than modules exposure for thin-film environmental Ionomer from offer protection PVB higher and followedhighest, EVA, by and TPU ionomer no water and silicone [164]. while store practically sion ionomer the whereas rate, foils show lowest. of is concentration the the PVB saturation The - TSI) show and water foils highest vapor thermoplastic (TPU the transmis The hand. other on the radiation due to UV transparency the decreases and waterone hand on the it as disperses stores and is important encapsulant The radiation. UV and humidity majorsion the are causes aging, and and Main, Germany: Kuraray Europe GmbH. Adapted and reproduced with permission.) with reproduced and Adapted GmbH. Europe Kuraray Germany: Main, am Hattersheim Technology Perfection, in Film—Solar PVB with Optimisation Module Trosifol—Solar 3.21 FIGURE modules abovesolar 450 ( nm [162] effective transparency application high the is in the wavelength material of window this of ionoplastics,polyolefins, (TSI). The advantage modified silicones PVB thermoplastic of and for PV TPU,with andcompetes modules, solar for thin-film encapsulation alternative, particularly tant composition. most chemical isimpor the PVB original their retaining thus on exposure heat, to meltproducts Thermoplastic withoutcell. cross-linking the solar embed firmly thus and material formarubber-elastic lightto UV on and/or exposure heat to cross-link component that silicones EVA, elastomer are two- products encapsulation and resins, cross-linked acrylate and The TPU materials. thermoplastic elastomers and cross-linked mainly today are used industrially and ucts The suitable- as encapsulationprod fewpolymer bymaterials glass film. front aPVB the from semiconductor photoactivemodules, the separated and layer substrate on aglass isdirectly applied 3.20 FIGURE Polyvinyl Butyral

Transparency of PVB in the range of maximum yield of silicium solar devices. (From Kuraray, (From devices. solar yield of silicium of maximum range the in of PVB Transparency Various types of solar module assemblies. module of solar Various types Cr

Transmittance (%) 100 ystalline module 20 40 60 80 200 0 Figure 3.21 0 0 800 600 400 Glass (b Glass PV Cells PV Gla ) [163]. However, for PV modules must stand corro also B B ss (front Wa ack) veleng So St So ) andard lar lar cell th (nm) PV la Ac PV Gl B yer PV as tive 001200 1000 B s B in ﬁlmmodule 1400 127 - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 In vacuum laminators, films are de-aired, pressed, and cooled; the cycle time is 8–20 min min the andforcooled;cycle 8–20 is pressed, time de-aired, are films vacuum laminators, In subsequent with autoclaving. acalendar abag or in in using de-airing process two-stage the or in EVA with than PVB sensitivity may from but acid, suffers release that PVB hydrolysis. acetic to with is less critical metallization Corrosion of the losses delamination. and transmission to lead that discoloration, especially processes, of degradation kinds components various with the easily impair may temperature day, athigh and night between humidity high gradients and temperature large doses, humidity. and irradiation High temperature, irradiation, by UV conditions mainly caused weathering hard in behavior components, polymeric of by degradation especially the the affected a key advantage [165]. remains be glass of also a PV reliability module can and performance The EVA, EVA. but PVB in solubility in higher being higher being diffusion with Adhesion of to PVB 128 ally it is also suitable to coat textiles to give water and stain resistance without affecting appearance, appearance, without affecting it suitable resistance ally is give also to coat to textiles stain water and wood. from phenolicwith of gives resins terpenes bleeding to excellent barriers discoloration for Combination coatings. against polyester is protected substrate polyurethane and The coating.the wood flexibility,to resistance, resistance impact adhesion, moisture and toughness, food additive for uses. indirect Administration US Drug of and the Food requirements extractability enables the meet to curing and linings, can and spray, printability. Application by and is made brush, proofness drum bed for fluidized dip, and used. phosphate, increasingly systems borate, or compounds, molybdates using zinc are chromium improved up about to 140°C. by toxicity about stoving the of of Because at temperatures concerns Adhesion phosphate holes is film. pin the in supplying ions also repair to binder chromate adhering pigment an in acorrosion-inhibiting as acts and surface plex metal of yields the phosphatizing the com Combination of metal pigment, asingle PVB, phosphoric chrome and in treatment. acid, locks. Wash effective is dam very bridges, and primer for of inhibition corrosion airplanes, ships, flexibility. and toughness coating tanks, in storage increases widely It is surfaces: and on metal used improves adhesion, cratering, It improves fast minimizes uniformity, drying. and coating metal to effective due adhesion good to obtain to inhibition corrosion wash as primers is used PVB metal, for [102,166,167]. improved by resistance corrosion dip-coating obtained protective for coatings In be can temperature atroom or cured baked, may air-dried, compositions. be that coating Films cards. watches, RFID application sound and sensors, coils, for motors stepping in quartz used are 110–140°C, temperatures, moderate or by solvent Such activation or methanol. wires ethanol with bonding,oven, or electric) air (hot resistance, heat with easily bonded be at can wire that from coats. liquid powdery in and It both is used or ureas. melamines, isocyanates, phenolics, with epoxies, reactive or cross-linking sites for combination, self-crosslinking, chemical hydroxyl The materials. enable groups of provide good wetting most and substrates thermosetting hydroxylthe the to be brought to sive connection can that in flexibility the to content properties and due on its to PVB excellent based are adhe adhesives, enamels, inks and paintings, Many coatings, 3.8.3 cycle (1 time min). even speeds, for short modules, with large-format machining high permits Rollsure. laminator an autoclavein and pres at aboutelevated 135°C.temperature laminated finally are modules The is temperature oven. ahot-air avacuum 100 in of in maximum mbar less and The than or rubber of bags plastic made in de-aired glass/glass glass, be safety can modules laminated as principle same the On for glass/glass thickness. on glass min modules, 8–25 depending and sheet glass/back PVB combined with nitrocellulose and plasticizer has been used in paint for paint leather. in used But been has gener plasticizer and nitrocellulose with combined PVB for acomponent as of is sealers used wood washPVB providing and holdout, coats intercoat iron) lead, solution PVB moisture- with foil tin, brass, (aluminum, increases metal Coating of surface give to resins combination awide with variety functional aloneor in is used PVB made coils overcoat to enamels so that stoving in may or wire wires used resins be magnet PVB single-stage vacuum in laminators processed of be PV can module, PVB type on the Depending m isc e llan e o u s

A pp lications Handbook of Thermoplastics Handbook - - - - Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 tion dosimeters [187].tion dosimeters sensors as humidity [129]. used were polyaniline Nanofiberswith salts)as dopant triflate [186] lithium and perchlorate, lithium radia sensors suchor as thiocyanate, [184,185], dye-sensitizedcells solar in devices (using iodide, electrochromic lithium and lithium of multilayerfacture devices electronic [182], even and [183], cells fuel in solid polymer electrolytes α nate with copper foil. PVB can also be a base for a base be hot also foil. melt copper with can nate PVB adhesives providing film clear a tough, prepregs of the phenolic joining lami in used are such mixtures required, are properties dielectric and resistance, blister adhesives board strength, where peel 160°C for printed-circuit In 15–30 min. at temperature and time together curing with pressed and heated are surfaces the temperature, room solvent the completely been After has leather, removed wood, cloth, materials. paper, other and at [168].matrix and adhesion fibertoward aluminum its of carbon stability improves that thermal carbon oxide amorphous and of ahybrid ofcursor aluminum coating nylon, wool, such cotton, as silk, rayon,mon viscose materials synthetics. textile other and com all practically to film a transparent color as applied be and feel, fabric. of can the drape, PVB ture energy, and even optical transmittance, provided that the processing temperature is lower temperature than processing the provided that energy,ture even and transmittance, optical frac strength, tensile at break, of plasticizer, amount possible, strain properties, including chemical Wang [189]. et al. is PVB plasticized close initial of Recovery those to the of properties with PVB reagentcoloration by was decolorization proposed of using and ethyl colored sheets PVB acetate (>0.5%) excess if itof alkali properties changes PVB dis for and A method separation is used. and leach plasticizers, can saponification the is that only problem technique The ofexpected. this be ofcan residues. glass is efficient, though saponification of Separation brushing plasticizers cal mechani solutionfinal water and stage, 60°C a first at alkali followedin separation by chemical effective [188] and More peeling. sophisticated techniques in mechanical cracking mechanical use sents colored (70% PVB 4% of by and glass PVB of impurities). is recovered laminated PVB from 2referscategory colorless to (2% PVB 96% and of PVB), of impurities 3repre category while (98% PVB categories. 1includes of Category any impurity), transparent of PVB, free three into unavoidable the and heat, step. and reprocessing radiation Recycled UV to is separated PVB mitted cycle life removal polymer, the the of prodegrading from of glass are sub the PVB PVB laminated issues for recycling the of main PVB. The of virgin that half could be price the though glass, than [79], tons/year about 120,000 be to is much PVB tions at waspresent, less estimated and recycled applica industrial including all sheets PVB of produced amount total investigations. the Indeed, it driven a lot and has of last few recycling the raised in of interest In wastebeen years, PVB has 3.8.4 such SiGe of inorganics as presence or FeSi various in studies degradation by many was demonstrated This suitable used. provided conditions that are ceramics performance of high- for binder manufacture the temporary it ideal sintering, is an no residue during virtually nickel and [175–177]. yttrium, cerium, chromium, titanium, Since zirconium, itsilica combusts with [169,170], alumina with tape green and slurry of ceramic [171,172], ferrites [173,174], titanate barium the level particles fine of minimize andto [14,162].roll, fuser overintegrity improvethe to film viscosity, increase to toners in binder asecondary plates. as serves It also offset printing and inks, pen conductive ribbons, as technology Actually, printer pastes, printing. printing many it in is used flexography. solventshigh-quality alsoandand soluble is fast-drying aromatic PVB high-speed in for and jetprinting, ink it improvesscreen, flexibility,gravure, used for inks andtoughness of adhesion, signs. road and decals, retroreflective license for films plates, in used beads glass the binds PVB adhesivewith strength. Polyvinyl Butyral -alumina, and Mixtures of PVB and phenolic resin are used as structural adhesives glass, for metal, bonding structural as used phenolic of are and resin PVB Mixtures pre as a and used fiber isopropanol wereby on carbon coating dip deposed aluminum and PVB Finally, power binding elasticity, owing and its to outstanding is suitable PVB for manufacture the it is soluble because solvents mild inks in and such esters, alcohols printing as and in is used PVB r e cycling γ -alumina [180],-alumina silver and [181]. ceramics glass manu the in used are tapes These

of PV B 2 [178,179], mullite, silica, 129 ------Downloaded By: 10.3.98.104 At: 19:32 28 Sep 2021; For: 9781466577237, chapter3, 10.1201/b19190-4 REFERENCES (see agents blends thermoplastics in toughening other with as Section 3.7.1). also and of effect aplasticizing [71]. because temperatures glass for Recycled used be laminated can PVB contents (8 moisture moderate wt%) with were higher PVB PVB, while suggested stand for can dry (below 150°C) Low temperatures processing tuned. be can amount but the expected be can cizers [36].step separation the in of used Loss plasti reagent are low of that alkaline and amounts 260°C 130

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