20

Protein Adhesives for Wood

Alan L. Lambuthy
Boise Cascade Corporation, Boise, Idaho, U.S.A.

I. INTRODUCTION Human beings have apparently had a propensity for gluing things together since the dawn of recorded history and probably before. By experimentation, we learned over time that certain natural products or extractives could develop bonds in wood of sucient strength to break in the material being glued rather than in the glue lm itself. These observations ultimately led to papyrus laminating, decorative wood veneering, and furniture and musical instrument assembly, practiced by the early Chinese and Egyptians and virtually every other civilization since that time using natures own glues [l3]. By todays standards, the ancient adhesive raw material choices were limited. Starch, blood, and collagen extracts from animal bones or hides were the principal early sources. Somewhat later, milk protein and sh skin extracts were discovered and included. Interestingly, vegetable proteins appear not to have been utilized as adhesives until recent times [4]. Tree pitch and petroleum bitumen were known and exploited as weatherproof coatings and caulks but not as adhesives, due to their plastic-ow behavior [5]; that is, the joints would creep and thus could not be used for structural support. Adhesive durability has always been a problem. Although starch and protein glues were able to maintain long-term adhesive strength when kept completely dry, none were to any signicant degree resistant to water or mold. Heat-cured blood glues and casein glues eventually provided some moisture resistance, but that was as durable as the technology of the times permitted. This fact limited the uses of adhesives strictly to interior or at least covered exterior applications from early historical times down through the Industrial Revolution and nearly to the present. From the middle of the nineteenth century onward, knowledge regarding more ecient means of dispersing and denaturing protein adhesives began to accumulate [6,7]. The results were signicant improvements in protein glue working properties, bond strength, and water resistance, but still well short of true exterior durability. The urgencies of World War I brought protein-based adhesives to their nearest attainment of this goal in the form of chemically denatured, heat-set blood glues. These were used to assemble, among other things, laminated wooden airplane propellers and structural components in support of the war eort [8]. In the early 1920s the rst of the phenolformaldehyde and ureaformaldehyde resin adhesives were developed [9,10]. These early resins were slow to cure and somewhat dicult
y

Deceased.

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to use, but they ushered in the era of thermoset polymeric adhesives and true exterior durability. The urgencies of World War II forced the rapid development of these and other synthetic resin glues for their water and weather resistance but left protein adhesive technology to evolve and ourish in applications for which interior durability was still adequate [11]. In the years following the war, the greatly expanded and partly idle petrochemical industry went looking for appropriate new markets. Among the opportunities identied were synthetic resin adhesive applications. Within a decade, these were converted from costly wartime adhesive specialties to bulk commodity glues. Throughout this synthetic resin expansion, however, protein adhesives held onto their interior durable product applications, due in large part to their unique combination of low cost and coldcuring capability or, alternatively, very fast hot press curing (about twice as fast as phenolics) [12,13]. This situation continued into the 1960s, at which time the price of petrochemically based adhesives had become so low that they literally displaced protein adhesives from their traditional interior markets. Specically, phenolic and ureaformaldehyde resins replaced blood, soybean, and starch glues in all plywood and composite wood panels; resorcinolformaldehyde resins replaced casein glues in lumber laminating and millwork applications; and poly(vinyl acetate) and acrylic emulsion glues replaced virtually all collagen adhesives (animal and sh bone/skin derived) from furniture, musical instruments, and general interior wood assembly [14]. Limited and specialized applications for protein glues, mainly in combination with synthetic resin polymers, continue to the present, however. These are discussed in the following sections. It is worth noting that protein glue technology in each of the application areas described above remains fully useful and industry approved in a backup sense and could be reintroduced rapidly if world petroleum resources were to be threatened again through events beyond national control, as in 1973. In this chapter we address three of the most widely used families of protein-based adhesives for wood: soybean, blood, and casein. The technology presented is drawn primarily from the years 1930 through about 1960, when the consumption and technical renements of these adhesives were at their peak. Soybean glues are discussed rst because they were often utilized in combination with blood or casein to yield adhesives of intermediate performance properties as well as being used alone.

II. A.

SOYBEAN ADHESIVES Raw Material Source and Preparation

Soybeans are legumes, the seeds of a low-growing eld vine. These vines are ancient in culture; the written record of their domestication in China dates back almost 5000 years [15]. From that time until now, soybeans have remained a very important agricultural crop for almost every temperate-climate civilization because of their unusually high content of both triglyceride oil and edible protein. To process soybeans into these useful products, the beans are dehulled and the oil is removed by crushing at very high pressure or by solvent extraction. If the resulting dry soybean meal is intended for food, it is heated to 70 C or higher to coagulate the proteins and caramelize the carbohydrates, thus improving their nutritional qualities. If the soybean meal is intended for adhesive use, it is processed at temperatures below 70 C to preserve the alkaline solubility of the proteins [16]. The protein content of oil-free soybean meal ranges from about 35 to 55% on a worldwide basis. However, the industrial grades are generally blended to yield a uniform
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protein content of 4452%, depending on the source. The other principal constituents of soybean meal are carbohydrates, totaling about 30%, and ash at 5 or 6% [17]. The moisture content after processing is quite low, usually less than 10%. Production experience has shown that to perform well as a protein glue, adhesivegrade untoasted soybean meal must be ground to an extremely ne our [18]. Typically, the dry extracted meal is ground or milled until at least 40%, and preferably 6080%, will pass through a 46-mm (325-mesh) screen. For easier quality control with ours of this neness, an alternative specic surface test method is available that determines average particle size in terms of surface area per gram [19]. For the range of mesh sizes recommended above, the corresponding specic surface values are about 30006000 cm2/g. B. Formulation

Soybean our will wet and swell in plain water but will not disperse to yield useful adhesive properties. For this purpose, treatment with a soluble alkaline material is necessary. Almost any organic or inorganic alkali will disperse wetted soybean our to some degree. However, soybean wood glues of maximum bonding eciency require dispersion with several percent of a strong alkali such as sodium hydroxide or trisodium phosphate [20]. The eect of this strongly alkaline treatment is to break the internal hydrogen bonds of the coiled protein molecules, literally unfolding them and making all their complex polar structure available for adhesion to wood. Although essential for adhesion, this alkaline dispersion process exposes the protein structure to gradual destruction by alkaline hydrolysis. Thus a dispersed soybean glue has a denite useful life, slowly losing viscosity and adhesive functionality over a storage period of 612 h. Although these strongly alkaline soybean glues are nearly colorless in an applied lm, they cause a reddish-brown stain on wood surfaces as they cure, due to alkali burn of the cellulose itself [5]. If a colorless glue line on wood is desired, the wetted soybean our must be dispersed with a less strongly alkaline material, such as hydrated lime or ammonia [21]. However, the adhesive bond strength of these low-color, mildly dispersed soybean glues is considerably less than that obtained with fully dispersed, highly alkaline formulations. Typical high- and low-alkali soybean glue formulations are listed in Tables 1 and 2.

Table 1

High-Alkali Soybean Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 1621 C Adhesive-grade soybean oura Pine oil or diesel oil defoamer: mix 3 min or until smooth in a counterrotating mixer Water at 1620 C: mix 2 min or until smooth Fresh hydrated lime (as a slurry in) Water at 1621 C: mix 1 min 50% Sodium hydroxide solution: mix 1 min Sodium silicate solution: mix 1 min Orthophenyl phenol or other preservative: mix 10 min
a

87.5 48.5b 1.5b 72.5 6.0 12.0 7.0 12.5c 2.5

44% protein, specic surface 30006000 cm2/g. Normally dry-blended for easier handling and dust control. c . 8.90% Na2O, 28.70% SiO2, 41 Baume
b

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Table 2

Low-Alkali Soybean Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 1621 C Adhesive-grade soybean oura Pine oil or diesel oil defoamer: mix 3 min or until smooth in a counterrotating mixer Water at 1621 C: mix 2 min or until smooth Fresh hydrated lime (as a slurry in) Water at 1621 C: mix 5 min
a b

112.5 48.5b 1.5b 75.0 15.0 25.0

44% protein, specic surface 30006000 cm2/g. Normally dry-blended for easier handling and dust control.

The additions of hydrated lime and sodium silicate solution in the high-alkali mix (Table 1) accomplish two purposes: (1) they help maintain a level glue viscosity for a longer adhesive working life, and (2) they improve the water resistance of the cured glue lm by forming some insoluble proteinates [22]. The starchy constituents of soybean our also disperse in the presence of strong alkali to become useful adhesive molecules contributing to dry bond strength. However, this starchy fraction also retains its well-known sensitivity to water and is considered primarily responsible for limiting the performance of soybean glues with respect to water resistance [23]. The nal addition of preservative shown in this formulation is essential in virtually all protein glues to provide mold resistance in high-humidity service. Without this protection, even heat-cured soybean adhesives will mold as the moisture content of the bonded wood approaches 20% [24]. Copper-8-quinolinolate, and copper naphthenate are among the few remaining preservatives permitted to be used in the United States at this time for wood products. Where the use of chlorinated phenols or orthophenyl phenol is still permitted, they are also very eective preservatives for protein glues at the addition level shown. In this case, the sodium hydroxide content of the glue formulation converts the water-insoluble chlorinated fungicides to their soluble sodium salts. Large quantities of this high-alkali soybean glue formulation were used to bond interior grades of softwood plywood between about 1940 and 1960 [13]. It was also used to some extent for assembling prefabricated wooden building components [11]. Its primary advantages were very low cost and the capability to bond almost any dry wood surface. It also oered real versatility in a bonding process because it could be hot pressed or cold pressed to promote cure. Appropriate pressing schedules for each curing mode are provided in tables that appear later in this chapter. The low-alkali formulation (Table 2) has been used widely as a briquetting binder for wood, charcoal, and other absorbent particles. It is particularly suitable for paper and softboard laminating, where a colorless glue line and minimum swelling of the glue lm on high-humidity exposure are desired [25]. It is not recommended for structural uses such as sheathing plywood because of its lower degree of protein dispersion and thus lower bonding strength. Substituting borax or monosodium phosphate for the hydrated lime dispersing agent will yield similar nonstaining glues. Over the years a number of denaturants or cross-linkers have been added to soybean glues to improve their water resistance, working life, and consistency. These may be roughly categorized as formaldehyde donors, sulfur compounds, and inorganic complexing salts.
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Table 3

Soybean Glue: Hot-Pressing for Interior Douglas Fir Plywood

(a) Pressing schedule Rough panel thickness (mm) Number of plies Panels per press opening 2 2 2 3 2 1 2 1 2 1 2 1 1 1 1 1 1 1 1 1 1 1 Platen temperature ( C) 110 116 121 127 127 116 132 110 121 110 121 116 121 127 132 127 132 132 132 132 132 132 Pressing time at full pressure (min) 3 3 3 5 4 3 434 3 6 334 6 4 4 414 4 5 5 6 7 7 8 9

4.8 6.4 7.9 7.9 9.5 11.1 11.1 12.7 12.7 14.3 14.3 15.9 17.5 19.0 20.6 20.6 23.8 27.0 30.2 33.4 36.5 39.7

3 3 3 3 3 3 3 5 5 5 5 5 5 5 5 7 7 and 9 7 and 9 7 and 9 9 9 9 and 11

(b) Glue application rates Core thickness (mm) 1.59 1.54, 2.82 3.18 3.63, 4.23, 4.76, 6.35 All constructions 5 or more plies, 20.6 mm and thicker On rough or warm veneer, add at least 12 g extra glue spread. (c) Other conditions 1. 2. 3. 4. Total assembly time per press load, 15 min. Veneer temperature not to exceed 43 C. Veneer moisture content not to exceed 8%. Not less than 14 kg/cm2 uniform hydraulic pressure. Mixed glue per single glue line (g/m ) 195 208 220 232 245
2

Each of these groups of compounds appears to react with the starchy constituents of whole soybean our as well as the dispersed protein molecules. Formaldehyde itself acts too rapidly and thus is dicult to control. Instead, such compounds as dialdehyde starch, dimethylol urea, sodium formaldehyde bisulte, and hexamethylenetetramine have been
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used successfully to toughen the cured glue lm and improve its water resistance [26,27]. Similarly, carbon disulde, thiourea, and ethylene trithiocarbonate, among the sulfur compounds [28,29], and the soluble salts of cobalt, chromium, and copper have been used to improve soybean glue working properties and adhesive performance [30,31]. These modiers are generally added last when preparing the glue. The range of addition of all such denaturants is 0.11.0% based on the weight of soybean our. Also, 520% of an aliphatic epoxy resin has been added to soybean glues, yielding signicantly improved durability, but the cost is high [32]. Similarly, alkaline phenolformaldehyde (PF) resins have been incorporated for both durability and mold resistance. Proportions have ranged from a straight soybean glue with a minor resin addition to a primarily PF resin glue containing a moderate quantity of soybean our [33,34]. Soybean protein is presently being evaluated as a costreducing adhesive constituent in phenolic and ureaformaldehyde resin binders for wood particle and cellulosic waste reconstituted products. C. Mixing, Application, and Pressing Soybean glues are very easy to mix, provided that they are wetted with plain water as a rst step. (If any form of alkali is present in the rst mixing water, the dry soybean our will form permanent lumps.) As with all protein glues, the rst mix is kept thick to break down any lumps of dry powder that may be present. The division of water additions in both formulations listed earlier demonstrates this mixing procedure. Once the soybean our particles have been uniformly wetted, further dilution and dispersion steps can follow without diculty. Water additions are adjusted to yield a mixed glue viscosity in the broad range of 50025,000 cP at 25 C, depending on purpose. Briquetting and paper laminating glues would typically be 5001000 cP, while cold-press plywood glues should be 10,00020,000 cp for best performance [35]. Hot-press formulations would be midrange. Particularly because of the heavy rst mixing stage and the high nal viscosities, an appropriate soybean glue mixer should have relatively strong, slow-turning blades plus a counterrotating scraper for continuous removal of glue buildup from the mixer walls. Low-viscosity soybean briquetting adhesives are generally applied by spray. Paper and softboard laminating glues are usually applied by curtain coater, knife, or indirect roller. High-viscosity plywood and lumber assembly formulations are fairly well limited to application by spreader roll or extrusion. For very small assembly jobs, soybean glue can easily be applied by brush. One of the real advantages of protein glues generally is their ability to be cured (under pressure) either hot or cold. Typical commercial schedules for each mode of cure are given in Tables 3 and 4. The cold-pressing schedule in Table 4 is the result of an interesting laboratory observation and subsequent industry-wide patent [35]. Alkaline protein glues, particularly soybean glues, lose water quite rapidly into adjacent dry wood surfaces. As a result, they gain sucient gel strength in 1520 min to permit removal of a glued wood assembly from its clamping device without loss of intimate contact between the glued surfaces. Cure is then completed over the next 612 h simply by placing the bonded products in storage at ambient temperatures with minimum handling. This method of cold pressing, called the no-clamp process, was used throughout the softwood plywood industry for many years. Prior to its introduction, all protein-bonded cold-press plywood was clamped for 68 h with bulky steel beams and turnbuckles. Because protein glues develop bond strength primarily by water loss over time, roll pressing has proved unsuccessful as a clamping method for wood products. The short, intense period of pressure simply squeezes the still-uid mix o the glue line without
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Table 4

Soybean Glue: Cold-Pressing (No-Clamp) for interior Douglas Fir Plywood

(a) Glue application rates Core thickness (mm) Mixed glue per single glue line (g/m2) 305318 313323 318330 325337 330342 330342 367

2.54 2.82 3.18 3.63 4.23 4.76 All constructions 5 or more piles, 20.6 mm and thicker For rough or warm veneer, and an extra 20 g over these spreads. (b) Other conditions 1. 2. 3. 4. 5. 6. 7. Hold press load 5 min after assembling last panel before applying pressure. Total assembly time limit per press load, 25 min. Veneer temperature not to exceed 43 C Veneer moisture content not to exceed 8% Use 1214 kg/cm2 uniform hydraulic pressure. Pressing time to be measured after gauge reaches full pressure. Pressure to be retained for 15 min.

aording sucient time for water loss and gelation. An exception is the soft rubber roll or brush roll lamination of paper to paper or paper to wood [36]. This can be accomplished at production speeds because of the extreme rapidity with which dry paper removes water from a protein glue lm. D. Blended Formulations As mentioned earlier, the single largest commercial use of soybean our in wood glues during the recent past has been as a blend with other adhesive proteins, mainly blood and casein, for bonding interior-grade plywood, doors, and millwork. These blended formulations exploit several unique properties of the soybean glues themselves and incorporate useful adhesive characteristics from the other protein materials. 1. SoybeanBlood Glues For example, a blend of soybean our with spray-dried soluble animal blood, a fairly expensive but very ecient adhesive protein, yields a glue with the best properties of each material [37]: namely, the cost becomes moderate and the consistency ideal for wood product assembly (slightly granular) because of the soybean our. The hot-press curing time is very short and the cured glue bonds are considerably more water resistant because of the bloods thermosetting properties. Fortunately, both proteins require the same neutral wetting procedure and strongly alkaline dispersion steps. They are otherwise compatible in all proportions, yielding a series of cost/performance-related adhesives. Soybean blood blend glues were by far the most widely used protein hot-press adhesives for interior structural plywood from the early 1940s until about 1960 [13]. Also, when the oil embargo
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Table 5

Low-Blood-Content Soybean Blend Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 1621 C Adhesive-grade soybean oura Dried soluble animal blood 75-mm Wood ourc Pine oil or diesel oil defoamer: mix 3 min or until smooth in a counterrotating mixer Water at 1621 C: mix 2 min or until smooth Fresh hydrated lime (as a slurry in) Water at 1621 C: mix 1 min Sodium silicate solution: mix 1 min 50% Sodium hydroxide solution: mix 5 min Orthophenyl phenol or other preservative: mix 5 min
a

100.0 36.0b 7.5b 5.0b 1.5b 110.0 4.0 8.0 20.0d 5.0 2.5

44% protein, specic surface 30006000 cm2/g. Normally dry-blended for easier handling and dust control. c 0.074 mm (200 mesh) and ner. d . 8.90% Na2O, 28.70% SiO2, 41 Baume
b

Table 6

High-Blood-Content Soybean Blend Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 1621 C Dried soluble animal blood Adhesive-grade soybean ourb 74-mm Wood ourc Pine oil or diesel oil defoamer: mix 4 min or until smooth in a counterrotating mixer Water at 1621 C: mix 2 min or until smooth Fresh hydrated lime (as a slurry in) Water at 1621 C: mix 1 min Sodium silicate solution: mix 1 min 50% Sodium hydroxide solution: mix 5 min Powdered hexamethylenetetramine: mix 3 min
a

80.0 35.0a 8.5a 5.0a 1.5a 195 4.0 8.0 22.5d 8.0 1.0

Normally dry-blended for easier handling and dust control. 44% protein, specic surface 30006000 cm2/g. c 0.074 mm (200 mesh) and ner. d . 8.90% Na2O, 28.70% SiO2, 41 Baume
b

of 1973 quickly placed phenolic resin adhesives on allocation through petrochemica1 restrictions, the plywood industry immediately returned to the use of soybeanblood hot-press glues for interior structural grades. Typical examples of low and high-bloodcontent soybean-blend glues are described in Tables 5 and 6. Both glues are ready to use when mixed and have a working life of 68 h at inside temperatures. Several points of dierence between these glues should be noted: 1. The water content of the high-blood-glue formulation is much larger, which osets most of the material cost increase. This is possible because the water

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2.

3.

4.

requirement of alkaline-dispersed blood is much higher than that of soybean our. The order of addition of alkaline dispersing agents in the high-blood mix is partially reversed. Experience has shown that this helps impart a more granular consistency to the dispersed blood, which is otherwise very slick and smooth. The nal addition of hexamethylenetetramine illustrates the use of a formaldehyde donor to partially denature or cross-link the dispersed proteins. This adds further granular character to the mixed glue, lengthens its working life, and improves the water and mold resistance of the cured adhesive lm. As with straight soybean glues, the low-blood-content formulation requires a mold-inhibiting ingredient to meet plywood performance standards, whereas the high-blood-content glue does not [24].

2. SoybeanCasein Glues Blends of soybean our with ground and screened casein also yield a very useful series of protein adhesives, in this case, mostly cured cold [38]. While alkaline-dispersed casein yields strong, water-resistant cold-cured bonds in wood, its sticky dispersed consistency does not permit the rapid water loss needed for quick-clamping procedures. By combining it with an appropriate amount of soybean our, the cold-press no-clamp process can be used. Formulations of this type have proved so successful for bonding plywood faces onto wooden ush-door cores and frames in a short cold-pressing cycle that the entire industry has employed these protein adhesives from about 1950 to the present [39]. As a special performance property, the bonds of soybeancasein door glues maintain strong adhesion in a re until the glue lines are literally charred away. Thus glues of this type are widely used to bond ush-design re doors. They are also excellent adhesives for millwork in general [40]. Some current formulations also contain minor amounts of blood. The formulation of the typical soybeancasein blend glue listed in Table 7 is quite dierent from any protein adhesive described thus far in that all ingredients, dispersing

Table 7

SoybeanCasein Dry Glue: Ingredients and Mixing Procedure Amount (kg)

Adhesive-grade soybean oura 250-mm Lactic acid caseinb Fresh hydrated lime 74-mm Wood ourc Granular sodium carbonate Granular sodium uoride Granular trisodium phosphate Pine oil or diesel oil defoamer Water at 1621 C Dry glue: mix 2 min, until smooth and thick; let stand 15 min or until thinning has occurred; mix until smooth Water at 1621 C: mix 2 min or until smooth
a

29.0 9.5 3.5 2.5 2.5 1.0 0.5 1.5 100 50 25

44% protein, specic surface 30006000 cm2/g. 0.250 mm (60 mesh). c 0.074 mm (200 mesh) and ner.
b

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agents included, are dry-blended into a single packaged composition that requires only the addition of water to prepare. The uniform oiling of al1 ingredients during the blending operation is a key, since it slows down the solution of the alkaline ingredients long enough for the soybean our and casein to wet out under reasonably neutral conditions. Then the alkaline agents dissolve. Highly alkaline dispersing conditions are provided by reaction of the sodium salts with lime to yield sodium hydroxide in situ plus insoluble calcium salts [6]. (The sodium hydroxide needed for this strongly alkaline dispersion step could not be included in a one-package composition because of its hygroscopic behavior). These sequential solution and dispersion reactions require some time for completion, which is the reason for the 15-min pause in glue preparation. The dry ingredients are blended intensively in an appropriate dry powder mixer while the defoamer is sprayed in to provide uniform distribution. Mixing directions are given in Table 7. The second water addition may be increased or decreased to obtain the nal viscosity desired. (A normal range is 40008000 cP.) Working life is 46 h at inside temperatures. Application rates must be determined by experience but will generally range from 245 to 345 g of mixed glue per square meter of a single glue line. While the soybeancasein blend glue can be used according to the short-cycle noclamp process on dry softwood, it will require 46 h of clamp time to cure to machining strength when used on dense hardwoods. Water removal from the glue lm is simply too slow on hardwoods to develop adequate early gelation. However, the ultimate bond strength is excellent. Note that this formulation represents about the maximum casein content at which short-cycle clamping is possible for softwood ush-door or millwork assembly. Above this level water loss is too slow, interfering with normal production rates through the press.

III.

BLOOD GLUES

Since soybeanblood blend glues were covered in the preceding section, in this portion of the chapter we deal only with all-blood adhesive compositions. A. Raw Material Source and Preparation

Historically, animal blood could be used for adhesives only in reasonably fresh liquid form. These glues performed well on wood. However, the very rapid spoilage rate of liquid blood imposed real limitations on the general availability and use of this adhesive raw material. It was not until about 1910 that techniques were developed for drying whole blood in commercial quantities without denaturing its protein content, thus maintaining its water solubility [41]. As a result, blood could be collected, processed, and stored indenitely for later use. The eect of this development was to stimulate rapid growth in the technology of blood-based adhesives, especially for wood, about the time of World War I. Virtually all the proteins in animal blood can be dispersed into useful adhesive form. These include the serum albumin and globulin and even the red cell hemoglobin [42]. The brin clotting substance is sometimes removed before drying (by agitation or acidication) because of its instability in solution. Thus, except for residual moisture content, dried blood is essentially 100% active adhesive protein. The principal North American bloods sold in quantity for adhesive uses are beef and hog, with lesser amounts from sheep and horses. Because of its high lysine content, poultry
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blood is utilized almost exclusively as a feed additive or binder and is seldom available otherwise. For adhesive purposes, there are signicant viscosity dierences relating to species among these dried bloods, beef being highest and poultry lowest [43]. Viscosity and water-holding properties are also inuenced by animal age, diet, activity, and other factors. As a result, industrial-grade dried soluble blood is generally blended in large quantities to provide average and reproducible properties for adhesive formulating. The method employed for drying blood is now entirely spray drying. (Formerly, a certain amount of vacuum pan-dehydrated blood was also available.) Spray-drying conditions relating to temperature, dwell time, and humidity can be adjusted to produce a wide range of blood solubilities [44]. Also, chemical denaturants such as glyoxal can be added to the blood solution prior to drying to further modify its adhesive characteristics [45]. Solubilities from about 20 to 95% can be prepared with 5% control. (Dried bloods below 20% solubility can only be redissolved in strongly alkaline solutions, which destroy a signicant portion of the adhesive proteins.) This controllable range of solubilities permits the formulation of blood glues with a variety of handling and performance properties. Generally speaking, the lower the solubility of a dried blood product, the more granular and water holding is its alkaline-dispersed form [46]. For instance, blood glues of 2040% solubility make excellent cold-press formulations (which must have a granular consistency) [42]. They also yield the most water- and mold-resistant (near-exterior) glue bonds when cured hot. By comparison, highly soluble bloods in the range 8593% yield very slick and livery alkaline dispersions of somewhat lower water-holding capacity. Soybean our is normally blended with these highly soluble bloods to produce appropriately granular glues. If soybean our is not used, they must be combined with a particulate cellulosic ller such as wood our or nutshell our to develop this functional consistency. Examples of these glue types are provided in the following section. B. Formulation

As with the soybean glues discussed previously, dried blood adhesives must initially be wetted or redissolved in plain water and then be subjected to one or more alkaline dispersing steps. Unlike vegetable proteins, however, high-solubility blood proteins can be dispersed and rendered strongly adhesive by more moderate alkaline agents such as hydrated lime or ammonia [47]. Especially with a denaturing compound added, these glues represented the most water-resistant adhesives available until the advent of phenolformaldehyde resins [5]. An example is shown in Table 8. This mix is unique in the quantity of denaturant it employs. The aldehyde reaction actually causes the blood protein to gel for a short period before thinning out again to a working viscosity level.

Table 8

Blood Glue: Ingredients and Mixing Procedure Amount (kg)

90% Soluble spray-dried animal blood Water at 1621 C: mix 3 min or until smooth Water at 1621 C: mix until smooth Ammonium hydroxide, sp. gr. 0.90: mix 3 min Powdered paraformaldehyde (sift in slowly while mixing) Allow mix to stand 30 min; mix briey until glue is uid and smooth.
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50.0 40.0 3060 3.0 7.5

Table 9

Dry Heat-Treated Blood Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 1621 C 20% Soluble spray-dried animal blood 74-mm Wood ourb Pine oil or diesel oil defoamer: mix 3 min or until smooth Water at 1621 C: mix 2 min or until smooth Fresh hydrated lime (as a slurry in) Water at 1621 C: mix 1 min 50% Sodium hydroxide solution: mix 10 min Sodium silicate solution: mix 5 min
a

150 37.5a 10.5a 2.0a 165.0 5.0 10.0 8.0 17.5c

Normally dry-blended for easier handling and dust control. 0.074 mm (200 mesh) and ner. c . 8.90% Na2O, 28.70% SiO2, 41 Baume
b

Table 10

Hot Water-Coagulated Blood Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 63 C 90% Soluble spray-dried animal blood 74-mm Wood ourb Pine oil or diesel oil defoamer: mix 10 min Water at 1016 C Pine oil or diesel oil defoamer: mix 2 min or until smooth Fresh hydrated lime (as a slurry in) Water at 1016 C: mix 2 min 50% Sodium hydroxide solution: mix 2 min Sodium silicate solution: mix 5 min
a

100.0 40.0a 9.0a 1.0a 175.0 1.0 3.5 7.0 7.5 17.5c

Normally dry-blended for easier handling and dust control. 0.074 mm (200 mesh) and ner. c . 8.90% Na2O, 28.70% SiO2, 41 Baume
b

The useful life is 68 h. This formulation can be cured hot or cold, but hot pressing yields the most durable bonds. The next resurgence of blood glue technology came during and after World War II. By that time, the highly alkaline multistep dispersing systems of soybean glues had become well established and were employed successfully with blood glues. Two examples utilizing low-solubility blood in typical plywood glue formulations are shown in Tables 9 and 10. The second mix (Table 10) demonstrates the use of hot water to coagulate the blood and lower its solubility during the mixing procedure [48]. Both these glues are excellent adhesives for interior-grade plywood when cured either hot or cold. Preservative or denaturant additions are not normally required to meet plywood performance standards. As a point of interest, blood glues are not aected by many of the protein denaturants used to improve the performance of soybean glues: specically, sulfur compounds and complexing salts [49]. However, they are very sensitive to aldehyde-acting compounds, and
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these have been employed at levels of 0.11.0% to yield improved consistency and water resistance. Typical of these are glyoxal, paraformaldehyde, methylol ureas, and formaldehyde addition compounds such as dialdehyde starch and sodium formaldehyde bisulte. A special class of blood protein denaturants, used primarily with higher levels of blood solubility, are the alkaline phenolformaldehyde (PF) resins. Low-molecularweight, low-alkali PF resins cause granulation of dispersed blood protein without much eect on viscosity, usually a reduction [50]. Highly advanced, high-alkali PF resins such as those used as plywood adhesives generally cause rapid thickening and gelation of dispersed blood glues if not employed with care [33,51]. Resins of intermediate advancement and alkalinity are almost passive to dispersed blood. These interactions have been exploited to formulate bloodresin glues for dierent hot-press applications at almost every level of combination. Two examples at the extremes of the range will suce (Tables 11 and 12). In the case of the low-resin-content formulation (Table 11), PF resin addition also functions as a preservative agent and was used widely for the purpose. This formulation is for hot pressing only. The bond-durability level can be characterized as mid-exterior. For the high-resin-content formulation (Table 12), a partial addition of the PF resin can be made just after the initial mix and before sodium hydroxide addition if more uidity is needed for propeller-type stirring. This formulation is more properly termed a blood-fortied exterior PF resin adhesive for hot-pressing plywood or laminated veneer lumber [52]. Even in quantities this small, the eect of the animal blood is to reduce the hot-press curing time by 2030% over that of phenolic resins used alone. For purposes of adhesive solid, calculation, the blood content can legitimately be included with the phenolic resin solids. A special application for which 80% soluble blood is particularly suited is its use in phenolic resin glues as a foaming agent to produce air-extended PF adhesives [53]. These are currently used to manufacture plywood on automated production lines. For this purpose, the mixed adhesive containing blood is put through a special high-speed stirring and air-injection system that lowers the specic gravity of the adhesive from about

Table 11

Low-Resin Blood Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 1621 C 20% Soluble spray-dried animal blood 90% Soluble spray-dried animal blood 74-mm Wood ourb Pine oil or diesel oil defoamer: mix 3 min or until smooth Water at 1621 C: mix 2 min or until smooth Fresh hydrated lime (as a slurry in) Water at 1621 C: mix 1 min Sodium silicate solution: mix 1 min 4550% Solids low to intermediate advancement PF resin: mix 3 min
a

87.5 25.0a 12.5a 11.0a 1.5a 200.0 3.0 6.0 22.5c 13.5d

Normally dry-blended for easier handling and dust control. 0.074 mm (200 mesh) and ner. c . 8.90% Na2O, 28.70% SiO2, 41 Baume d Georgia-Pacic 3195, Borden Cascophen 335-1, Neste CB 118.
b

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Table 12

High-Resin Blood Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 1621 C 74-mm Nutshell oura Winter wheat our 90% Soluble spray-dried animal blood Diesel oil defoamer: mix 5 min or until smooth 50% Sodium hydroxide solution: mix 2 min Granular sodium carbonate: mix 15 min 43% Solids highly advanced PF resin: mix 5 min while cooling the glue at 2127 C
a b

250.0 75.0 25.0 17.5 2.5 28.0 10.5 610.0b

0.074 mm (200 mesh) and ner. Georgia-Pacic 5763, Borden Cascophen 318-G, Dynea CB 303.

Table 13

Foamable Glue: Ingredients and Mixing Procedure Amount (kg)

Water at 1621 C Industrial wheat our 80% Soluble spray-dried animal blood: mix 7 min PF plywood resin 50% Sodium hydroxide solution: mix 15 min PF plywood resin 50% Sodium hydroxide solution: mix 2 min Surfactant: mix 2 min or until smooth
a b

170 50 20 110a 12 275a 5 1b

43% solids phenolic resin; Borden Cascophen 3136, Dynea CB 305, Georgia-Pacic 4922. Emersol or equivalent.

1.0 to 0.2 with very ne air bubbles. The low-density adhesive foam is then extruded onto passing veneer surfaces, which are assembled and hot pressed to produce exterior grades of plywood. (Recycled glue is deformed and recirculated.) The primary advantage of this kind of adhesive is lowered cost: for example, savings up to 25% over that of conventionally applied phenolic adhesives. A typical foamable glue mix is described in Table 13. C. Mixing, Application, and Pressing As the formulations show, straight blood and soybeanblood blend glues are prepared in generally the same sequence and manner as outlined for soybean glues. Finished glue viscosity ranges are somewhat lower, typically 50008000 cP for hot-press formulations and 800020,000 cP for the thicker and grainier cold-press glues. Glue life at room temperature is 48 h: the cooler, the longer. With respect to application methods, blood glues can be spread on wood surfaces by most conventional means. These include roller, knife, and extrusion but do not include curtain coating or spray, for which the glues must be thinned below practical lm retention levels. The major advantage of alkaline-dispersed blood glues over all other wood glues except resorcinol-based synthetic resin adhesives is their sensitivity to heat, resulting in extremely
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fast hot-press curing times [54]. This property is of sucient importance to warrant reproducing an entire plywood hot-pressing schedule for purposes of comparison. The commercial blood glue pressing times shown in Table 14 are literally half those of current phenolic plywood resin adhesives. They are also signicantly faster than those listed earlier

Table 14

Blood Glue Hot-Pressing Schedule for Interior Douglas Fir Plywood Glue spread per single Minimum glue line stand timea (g/m2) (min) Pressing time (min at full pressure) 110 C 116 C 234 1 3 7 134 414 134 4 6 214 6 2 7 3 7 3 4 414 5 4 6 127 C 114 234 6 1 334 134 414 2 5 214 6 2 6 3 334 334 414 334 414 414 6 7 7 7 8 9 10 12 138 C 1 214 514 114 3 1 4 134 5 2 514 114 5 2 314 3 334 314 4 4 5 5 6 614 6 7 8 9

Panels Rough panel thickness Number per press (mm) of piles opening

6.4 3 2 171 3 3 7.9 3 1 183 3 134 7.9 3 2 183 3 3 7.9 3 3 195 3 9.5 3 1 195 3 134 9.5 3 2 195 3 11.1 3 1 208 3 2 11.1 3 2 208 3 11.1 5 1 171 3 3 11.1 5 2 171 3 12.7 5 1 183 3 234 12.7 5 2 195 3 14.3 5 1 195 3 234 14.3 5 2 208 3 15.9 5 1 195 3 3 15.9 5 2 208 3 17.5 5 1 208 3 4 17.5 7 1 208 3 414 19.0 5 1 208 3 19.0 7 1 208 3 20.6 5 1 208 3 20.6 7 1 208 3 22.2 7 1 208 3 23.8 7 and 9 1 220 4 25.4 7 and 9 1 220 4 27.0 7 and 9 1 232 4 28.6 7 and 9 1 232 4 30.2 7 and 9 1 232 4 33.4 9 1 244 5 36.5 9 1 244 5 39.7 9 and 11 1 244 5 Other conditions: 1. Total assembly time limit per press load, 16 min. 2. Veneer temperature not to exceed 43 C. 3. Veneer moisture content not to exceed 8%. 4. On rough or warm veneer, add at least 12 g of extra glue spread. 5. Not less than 12 kg/cm2 uniform hydraulic pressure.
a

Stand time after assembling last panel before loading press.

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for soybean glues. This hot-pressing schedule is suitable for all straight blood adhesive formulations and also for soybeanblood blend glues containing at least half blood as the active protein ingredient. Blood and soybeanblood blend glues of appropriate high viscosity and granular consistency can be pressed cold according to the schedule shown for soybean glues. For this purpose they must contain a terminal addition of about 5% preservative based on dry glue weight in order to meet product standards for mold resistance [24].

IV. A.

CASEIN GLUES Raw Material Source and Preparation

As with blood, the adhesive qualities of casein curd from milk were recognized in relatively ancient times. Mixed with a simple alkali such as lime, casein protein became an important adhesive for furniture and paint pigments and the preferred sizing agent for the canvas of Renaissance paintings [6,55]. Medieval furniture assembly was divided between casein glues and animal gelatin adhesives made from boiled extracts of bone and hide. The gelatin glues were applied to joints as a hot solution and gained bond strength almost immediately on cooling. The casein glues required much longer clamping times to develop adhesion by water loss and insoluble caseinate formation. However, the casein glues had true water resistance, whereas the animal gelatin glues remained forever sensitive to even slight moisture and heat exposure [5]. Thus casein tended to be used where durability was required. This association with water resistance has remained a favorable performance factor for casein glues down to the present. Casein protein is recovered from skim milk by acid precipitation to pH 4.5. Mineral acids may be used or the milk can be cultured with bacteria that convert lactose (milk sugar) to lactic acid, which in turn precipitates the casein. The precipitated protein curd is washed free of acid with hot or cold water and is then dried and ground. The commercial designation for casein often includes its method of acid precipitation (e.g., lactic acid or sulfuric acid casein). Since industrial casein competes directly with the worldwide food uses of milk and its proteins, the price of casein tends to vary widely as the supply/demand economics of milk products rise and fall. In recent years, the cost has remained well over $2 (U.S.) a pound. Even at this price, however, certain casein blend and specialty glues continue to hold a signicant place in current markets.

B.

Formulation

For adhesive uses, the particle size of ground casein is normally controlled within the range of about 250500 mm [56]. Particles coarser than 500 mm (30 mesh) may not dissolve and disperse completely during glue preparation. Those much ner than 250 11 mm (60 mesh) tend to form immediate lumps on wetting, even if oiled. For single-package casein glues (by far the most widely used type), preliminary oiling of the dry ingredients is a very important manufacturing step. It helps prevent the pickup of atmospheric moisture by alkaline salts in the dry composition followed by premature attack on the casein during storage. Oiling also slows down the solution of these salts in water at the time of glue mixing, thus allowing the casein particles to become wetted and lump-free in reasonably neutral water.
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The lime content of casein glues is similarly important. A high percentage of lime (above 30% of dry casein weight) ensures maximum water resistance of the cured glue lm but sharply reduces mixed adhesive working life. A lime content below 10% provides a long working life and adequately strong dry bonds on wood but signicantly reduces moisture resistance. Most commercial adhesive formulations balance these properties by utilizing lime additions in the range 1525% [57]. As with blood and soybean our, the maximum adhesive capability of casein is attained only by complete aqueous dispersion of the folded protein molecules with a strongly alkaline inorganic salt such as sodium hydroxide [56]. Since sodium hydroxide cannot be incorporated successfully into a dry adhesive composition, it is quickly produced on mixing through a double decomposition reaction between calcium hydroxide and strongly ionized but less alkaline salts such as sodium uoride, sodium carbonate, and trisodium phosphate. (The residues from this reaction are insoluble calcium compounds.) The viscosity and consistency of casein glues can be altered substantially by reaction with most of the classic protein denaturants such as sulfur compounds, formaldehyde donors, and complexing metal salts [6,56]. One or more of these are frequently used as manufacturing control to oset the natural variability of casein and produce glues of uniform properties. The water resistance of cured casein glues is also improved by moderate denaturing. Finally, to provide mold resistance adequate for interior and covered exterior structural requirements, a fungicide must be added to casein glues [40,58]. In this case there is no excess of sodium hydroxide in the glue composition to convert a water-insoluble fungicide to its soluble sodium salt. Therefore, it is added as a prepared soluble salt in order not to upset the fairly precise alkaline balance in the dry glue composition needed to fully disperse the casein. Sodium orthophenylphenate and sodium pentachlorophenate are examples. The casein adhesive formulation described in Table 15 embodies all the foregoing technology. The dry ingredients are intensively blended in an appropriate dry powder

Table 15

Casein Dry Glue: Ingredients and Mixing Procedure Amount (kg)

500250 mm Lactic acid casein 500250 mm Sulfuric acid casein 74-mm Wood oura Fresh hydrated line Granular trisodium phosphate Granular sodium uoride Powdered dimethylol urea Diesel oil defoamer Sodium orthophenylphenate or other preservativeb Water at 1621 C Dry glue: mix 2 min, until smooth and thick Let stand 15 min or until thinning has occured; then mix 2 min or until smooth.
a b

15.0 15.0 5.0 6.5 4.0 2.0 0.05 1.45 1.0 100 50

0.074 mm (200 mesh) or ner. Dowicide A, Dow Chemical Co.

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mixer while the defoamer is sprayed in to provide uniform distribution. The dimethylol urea addition, a protein denaturant, is variable for glue viscosity control. The small adjustment is made in the defoamer. Mixing directions are provided in Table 15. The nished glue viscosity should be in the range 4000 to 8000 cP at room temperature, thickening gradually over several hours and attaining a rm gel overnight. In a totally dierent area of application, casein adhesives for paper sizing, chipboard laminating, and label gluing are more nearly casein solutions [59,60]. They are simple dispersions with ammonia or borax at moderate pH and low viscosity. They are frequently combined with latexes or soluble rosin derivatives for special performance improvements [59]. C. Mixing, Application, and Pressing Casein glues for wood pass through an early thick-consistency stage that requires fairly strong agitation to reduce them to a uniform and lump-free state. The mixer should be equipped for sidewall scraping to work thickened glue continuously back into the stirred composition. Counterrotating paddle mixers and bread dough mixers have proved ideal for this purpose. Because of their thick, sticky consistency, casein glues are generally applied to only one of a mating pair of wood surfaces by roller, knife, or extrusion. Adequate adhesive wetting and transfer occur when the wood surfaces are brought together. The stickiness of alkaline-dispersed casein glue provides two of its best performance attributes: long assembly-time tolerance and wipe resistance (diculty of removal). A lm of casein glue on dry lumber, for example, may allow an open/closed assembly time of 12 h before clamping is required. This property is especially useful in the timber laminating industry, where it permits many pieces of lumber to be stacked over each other, adjusted for position, and assembled into large, complex laminated beams [61]. This long assembly tolerance plus the gap-lling and wipe-resistant capabilities of casein glues made them the outstanding choice for laminated structural wood products from the mid-1930s onward. Todays phenolresorcinolformaldehyde laminating adhesives, which ultimately displaced casein glues on the basis of exterior durability, could still use a large measure of these working properties of casein glues. While casein glues can be heat cured and were employed in the past to make hotpress plywood, most of the high-volume bonding applications have involved cold pressing. Casein glue lms are adequately cured by water loss and insolubilizing of the proteins through various chemical reactions at room temperature [62]. Heating does not yield signicantly improved water resistance. Except for soybeancasein blend glues, which take on the granular consistency of the soybean constituent, the inherent stickiness of straight casein glues dictates a fairly long clamping time to bring about water loss and adhesive hardening. Progressive shear tests have shown that these glues develop about half their dry strength in 3 h and substantially all of it in 68 h at room temperature. However, moisture resistance continues to improve for several days [63]. As mentioned previously, another performance attribute of casein glues that recommends their use in structural wood laminates is re resistance [64]. While all three of the proteins discussed in this chapter burn to a char before losing bond strength, casein adhesives appear particularly durable in this respect. Thus casein glues remain the adhesives of choice for the economical assembly of wood-based re doors of ush and panel designs. In yet another attribute, the combined adhesive strength and toughness (as opposed to brittleness) of casein glue lms has made them an ideal bonding agent for
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wooden sporting equipment and other applications required to withstand exing, vibration, and shock, such as racquets, hockey sticks, and shing rods [6,65].

V. OTHER PROTEINS Reference was made to the historical use of collagen glues derived from the gelatin extracts of animal bones and hides. This does not properly indicate the true importance to the wood industry of these materials. From ancient times to the present, animal glues have in fact remained one of the primary assembly adhesives for wooden furniture, cabinets, and musical instruments [66]. Applied as a hot, viscous solution to furniture joints, they rapidly develop gel strength on cooling that permits the prompt removal of clamping pressure. On subsequent drying, these glues cure to resilient, high-strength bonds between wood surfaces, especially those involving end grain. Animal glue bonds are strong and permanent as long as they are kept dry and reasonably cool but are subject to softening and fungicidal attack when moistened or heated. Water and temperature resistance can be improved through the incorporation of most of the protein denaturants listed earlier [67,68]. Animal glues are used widely in a variety of ways with paper. For example, they have been the dominant adhesive for rewettable gummed paper tapes, labels, and envelope seals [69]. They are an important coadditive with synthetic wet-strength resins and rosin sizes for coated paper products [70]. They have been a primary binder for the grit that forms sandpaper [71]. In contrast to their widespread use in furniture and paper products, animal glues have not proved useful as structural adhesives for wood. When used as the principal protein constituent, their water sensitivity is excessive compared with other available proteins. When combined with soybean, blood, or casein, animal gelatin glues are completely hydrolyzed and destroyed by the strong alkalies required to disperse these proteins. In addition, they soften when severely heated, which, by law, prohibits their use in structural wood products [5]. Although in recent years animal glues have been replaced substantially by the newer synthetic adhesives, particularly the vinyl and acrylic emulsions, large quantities are still sold in dry and stable liquid forms for furniture assembly or repair and paper bonding applications. Generally similar comments can be made with respect to sh skin adhesive extracts regarding these and other wood gluing applications. Fish skin glues are normally prepared in stable liquid form through mild acid hydrolysis and are frequently combined with animal glues for improved rewettability, tack, and adhesion of paper to glass or metal surfaces [72]. They dier from animal glues in one important respect: namely, they will not soften at elevated temperatures, especially when treated with aldehydic or polyvalent metal ion cross-linkers. Thus, in addition to the more conventional paper bonding applications, this property has created a major eld of use for sh gelatin extracts as durable but temporary protective coatings and light-convertible photoresist lms [73]. Other vegetable protein sources are occasionally mentioned as substitutes for soybeans. These have included cottonseed meal, peanut our, Alaska pea, and rapeseed meal, to name just a few. Although they do contain 2535% useful protein substance, they have never made signicant inroads on soybean our for wood-gluing applications on the basis of comparable performance. However, they can be used and are prepared for adhesive purposes in the same manner as soybean our itself.
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