Patent ID: 12234607

DETAILED AND EXEMPLIFYING DESCRIPTION OF THE INVENTION

In the following, a detailed description of invention methods and products are outlined together with embodiments of the invention. Wheat bran and oat husk contains cellulose, lignin, hemicelluloses (xylans and arabinoxylans), phenolic compounds such as ferulic acids, minerals and proteins. The mechanical and alkaline pre-treatments facilitates the extraction of the hemicelluloses and present invention exploit their potential as a bioadditive to contribute to an increase in mechanical properties of the produced biocomposites. Several different methods of preparing bioadditives with pre-treatments were tested and different cellulose fibers were also investigated. All the experiments are summarized in the tables below.

Different Pre-Treatments

Reference: 25 g of CTMP was disintegrated in 2 L of tap water at 30.000 rpm using a PTI Austria disintegrator. Hand sheets were made using Rapid Köthen. After formation the wet hand sheets were pressed with 10 tons pressure for 5 minutes and dried for 10 minutes at 95° C. Final oven drying at 170° C. for 5 minutes. Mechanical properties was measured using a Testometric M25-2.5AT.

Pre-treatment: Pretreatment of wheat bran from Lantmännen was performed according to the table below. An Ika Ultra Turrax was used for the mixing of 5 g wheat bran with 35 g of water containing the different chemicals in Table 1. The mixing time was 30 min and the speed was adjusted to 2 different levels. After the mixing was completed the wheat bran was added to the CTMP pulp. Hand sheets were produced exactly the same way as the reference except that 20 g CTMP instead of 25 was used.

TABLE 1WheatMixingCTMPbranAdditivespeed(g)(g)(g)Procedure(rpm)Ref25———a)205——b)205—6.000c)205—17.000d)2050.5% NaOH—e)2050.5% NaOH6.000f)2050.5% NaOH17.000g)2050.5% K2CO36.000h)2055% citric acid6.000i)2050.5% H2SO46.000j-1)2052% NaOHseparated6.000filtratej-2)2052% NaOHwheat bran6.000fractionk)2051% NaOH6.000l)2052.5% NaOH6.000m)2055% NaOH6.000

TABLE 2Standard deviation is given in parenthesesStrainStressYoung'sWeightat peakat peakmodulus(g)(%)(MPa)(MPa)Ref24.142.144(0.228)11.21(1.025)760.7(56.84)a)23.42.088(0.383)10.34(1.254)721.22(46.605)b)22.632.336(0.218)14.05(0.706)905.6(29.431)c)22.542.627(0.439)17.25(1.80)974.66(48.69)d)22.812.311(0.123)15.37(0.357)932.77(21.624)e)22.432.381(0.497)17.01(1.99)1015.19(48.80)f)21.902.488(0.29)21.54(2.375)1258.419(19.42)g)23.132.032(0.393)12.54(1.79)785.629(36.78)h)Not1.813(0.277)9.16(1.03)663.521(35.72)measuredi)23.202.01(0.339)11.04(1.241)713.762(11.99)j-1)19.602.564(0.237)19.26(0.974)1129.8(41.041)j-2)21.191.978(0.214)12.38(0.987)842.91(24.180)k)22.012.63(0.388)17.886(1.33)1075.682(33.805)l)21.972.221(0.256)15.197(1.075)999.924(51.518)m)21.612.51(0.515)18.091(2.455)1210.492(24.247)

No increase in strength was observed for the non-pretreated wheat bran without mechanical stirring (a, table 2). However, compatibility between the fibers and the wheat bran was good and the reduction in fiber usage was about 20%. Mechanical mixing alone of wheat bran without additives increased strength (b and c, table 2). More intense mixing gave higher strength for the hand sheets. Sodium hydroxide pre-treatment (0.5%) gave higher strength compared to neutral conditions. Also here the amount of mixing had an effect on the strength. More intense mixing gave stronger hand sheets (d, e and f, table 2). Acidic pre-treatments had no effect on the final strength (h and j, table 2). In one experiment (j-1 and j-2, table 2), the particles were separated from the solution after the 0.5% sodium hydroxide pre-treatment. Hand sheets were made from both the solid fraction and the water soluble fraction. It is clear that most of the strength increase comes from the dissolved material from the wheat bran pre-treatment (j-1, table 2). Hemicelluloses such as Arabinoxylans are probably extracted from the wheat bran during the pre-treatment and these polysaccharides adsorb to the cellulose fibers in the “wet end” during the paper making, with improved mechanical properties of the produced hand sheets. Different sodium hydroxide concentrations did not have a significant effect on the hand sheet strength (k, l and m, Table 2).

Different Fibers

Wheat bran was treated with 0.5% NaOH. A Water-wheat bran ratio of 7:1 was used. Mixing was performed at 20.000 rpm for 30 min using an Ika Ultra Turrax. 40 g of this pre-treated wheat bran was mixed with 20 g of different pulps according to the Table 3 below. Hand sheets were produced as described in the section above. 20 g of the pulp together with the pre-treated wheat bran was disintegrated in 2 L of tap water at 30.000 rpm. Hand sheets were made using Rapid Köthen. After formation the wet hand sheets were pressed with 10 tons pressure for 5 minutes and dried for 10 minutes at 95° C. Final oven drying at 170° C. for 5 minutes. 25 g of pulp was used as a reference without wheat bran.

TABLE 3A strength increase was observed for allthe pulps with pre-treated wheat bran.WheatStrainStressYoung'sbranWeightat peakat peakmodulus(%)(g)(%)(MPa)(MPa)CTMP—24.142.1411.21760.7CTMP2021.922.617.42989Bleached—24.943.7516.841109.2soft woodkraft pulpBleached2022.585.2324.941407.1soft woodkraft pulpUnbleached—24.802.8616.271136.1soft woodkraft pulpUnbleached2022.934.7526.861512.1soft woodkraft pulpBleached—24.752.3519.211415.7hard woodkraft pulp(birch)Bleached2023.024.0032.61800.7hard woodkraft pulp(birch)Dissolving—24.212.406.4481.3pulp(Domsjo)Dissolving2022.283.099.46642.5pulp(Domsjo)Abaca24.614.7221.521142Celtex BTCFAbaca2022.615.6227.571343Celtex BTCF
Different Additives Together with Pre-Treated Wheat Bran

The table below (Table 4) describes how different additives added in the “wet end” together with CTMP pulp and pre-treated wheat bran affects the final composite materials. Cationic starch further improves the mechanical properties compared to the wheat bran reference. AKD added as an emulsion also improved the strength and dramatically improved the hydrophobicity resulting in a Cobb60 value below 20. Old wheat bran containing preservatives stored for two months at room temperature gave lower strength increase compared to freshly prepared pre-treated wheat bran. The reason for this could be that the polysaccharides improving the strength, degrade over time. Antifoaming agent (Dispelair CF56) in the formulation lowers the strength of the produced hand sheets.

TABLE 4StrainStressYoung'sAdditiveWheatWeightat peakat peakmodulusCobbamountCTPMbran(g)(%)(MPa)(MPa)60Ref—20 g5 g21.922.617.42989896(80%)(20%)Cationic0.3 g20 g5 g22.472.9223.751275—starch(80%)(20%)(solbondPC170)AKD0.8 g20 g5 g2.9520.01110819(80%)(20%)Old wheat5 g20 g21.922.2513.0821.1—bran(20%)(80%)(180827,0.1% acticidepreserved)Dispelair1 g20 g5 g22.082.2612.12820.6—CF58(80%)(20%)
Different Concentrations of Pre-Treated Wheat Bran and CTMP Pulp.

Different amounts of pre-treated wheat bran was used in the experiments below demonstrated in Table 5. The wheat bran was pre-treated in the standard way by homogenizing for 30 min using an Ika Ultra Turrax at 17.000 rpm with a sodium hydroxide concentration of 0.5%. Different amounts of this pre-treated wheat bran batch was used with CTMP according to the table below. A strength increase is observed with up to 50% wheat bran. Then the strength goes down. Foaming is also increased with increasing wheat bran amount. A too high wheat bran fraction (99%) makes the material too weak and the final hand sheet could not be removed from the paper making wire without falling apart. A drop in weight of the produced hand sheets was also observed. This is caused by the increasing amount of soluble products that do not adsorb to the cellulose fiber.

TABLE 5WheatStrainStressYoung's% WheatCTPMbranWeightat peakat peakmodulusbran(g)(g)(g)(%)(MPa)(MPa)Comment025024.142.1411.217605%23.751.2523.652.1012.6680310%22.52.523.162.0414.2093020%20521.922.617.4298950%12.512.518.892.7725.61482Foaming75%6.2518.7516.191.9814.941064Foaming99%——————Sampletoo weak
Pre-Treated Oat Husk Powder and the Formation of Birch Kraft Pulp Composites.

Pre-treatment of oat husk was performed in a similar way as the pre-treatment of wheat bran to prepare the bioadditive grinded oat husk in the form of fine powder was mixed in 0.75% NaOH at a water solid ratio of 8:1. Oat husks were grinded to oat powder prior to use but could also be used as the mixing was performed using an Ultra Turrax for 30 min. 12.5 g (dry weight) of this slurry was mixed with 12.5 g of the birch pulp and disintegrated as described in the previous sections. Hand sheets were produced as described and mechanical properties were measured. The Tables 6 and 7, below, describe the ingredients for each sample. Foaming was observed during the usage of oat powder. Therefor a commercially available defoamer was used in these examples.

TABLE 6Amountbirch pulp(g)Oat powderAdditive 1112.5 g112.5 g pre-treated oat powder1 g Dispelair CF56(12.5 g dry weight)212.5 g12.5 g oat powder1 g Dispelair CF56312.5 g225 g pre-treated oat powder1 g Dispelair CF56(25 g dry weight)412.5 g337 g pre-treated oat powder1 g Dispelair CF56(37 g dry weight, washed anddecanted 4 times, solids mixedwith birch kraft pulp)

TABLE 7StrainStressYoung's modulus(%)(Mpa)(Mpa)Blank (birch)2.3519.211415.715.8433.42147123.6910.9761635.3925.51108444.1914.73695

A strength increase is observed in Table 5 with using 50% pre-treated oat husk powder.

In conclusion, the invention described here is a biocomposite material based on wheat bran and/or oat husk and cellulose. In addition to lowering the costs due to lower usage of fibers an increase in mechanical properties can be obtained by the different pre-treatments, especially the alkaline ones.